ࡱ> &}~|qWXYZ[ T U V W X Y R C~M bjbj== WWGlDDDDDDDD U U U WXtӋ 6Z By@yyyyyy$݌ P8UDyyyyy8|DDyy|||yFDyDy|y||DDy*Z `Y愭O Uy\0ӋMy>M|DDDDSupplementary Material for Progress Towards the Total Synthesis of Ingenol: Construction of the Complete Carbocyclic Skeleton Haifeng Tang, Naeem Yusuff and John, L. Wood* Sterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107 Organic Letters. ______________________________________________________________________________ Materials and Methods Unless otherwise stated, reactions were performed in flame-dried glassware under a nitrogen atmosphere using freshly distilled solvents. All commercially-obtained reagents were used as received. Analytical thin-layer chromatography (TLC) was performed using silica gel 60 F254 precoated plated (0.25 mm). Silica gel (Particle size 0.032-0.063 mm) was used for flash chromatography. High-pressure liquid chromatography (HPLC) was performed with either a rainin Microsob 80-199-C5 or 80-120-C5 column. 1H and 13C NMR chemical shifts are reported as  values relative to internal tetramethylsilane. Melting points are uncorrected. High-resolution mass spectra were acquired at The University if Illinois Mass Spectrometry Center. Single crystal X-ray analysis was performed by Dr. Susan Degala (Yale University). ______________________________________________________________________________ Preparation of 3-component adducts 6a and 6b.  EMBED ChemDraw.Document.4.5  A solution of lithium dimethylcuprate in anhydrous ether (12 mL) was prepared from CuI (481 mg, 2.5 mmol, 2.0 equiv) and 1.4 M MeLi solution in ether (3.6 mL, 5.0 mmol, 4.0 equiv). After stirring at 0C for 15 minutes, an ether (6 mL) solution of 5 (265 mg, 1.3 mmol, 1.0 equiv) was slowly added into the reaction flask. The mixture was allowed to stir at 0C under N2 for 40 minutes. A mixture of THF (4 mL) and HMPA (5 mL) was injected into the reaction solution, followed by rapid addition of allyl iodide (3 mL, large excess). The reaction was kept stirring at 0C for one more hour. The reaction mixture was poured into 10% NH4OH solution, and the product was extracted with ether. The extraction was washed with water and brine. After drying with MgSO4, the solvent was removed under reduced pressure. The residue was purified by flash chromatography (40:1 Hexanes:EtOAc eluent). First to elute was 6a (285 mg, 43% yield): 1H NMR (500 MHz, C6D6) d 6.35 (dddd, J = 17, 11, 9, 5.0 Hz, 1H), 5.17-5.24 (m, 2H), 3.32 (s, 3H), 3.26 (ddt, J = 14, 5, 2 Hz, 1H), 2.70 (dd, J = 12, 6 Hz, 1H), 2.65 (dd, J = 14, 9 Hz, 1H), 2.61 (t, J = 11.5 Hz, 1H), 2.12 (dt, J = 15.5, 11 Hz, 1H), 1.96 (ddtd 11, J = 7.5, 7, 1.5 Hz, 1H), 1.72 (ddd, J = 15, 6, 1.5 Hz, 1H), 1.32 (d, J = 7 Hz, 3H), 1.07 (s, 3H), 0.99 (s, 3H), 0.72 (ddd, J = 11, 9, 6 Hz, 1H), 0.57 (ddd, J = 11, 9, 6 Hz, 1H); 13C NMR (400 MHz, C6D6) d 204.6, 172.3, 136.4, 118.1, 67.2, 51.9, 39.3, 39.2, 38.8, 30.6, 28.7, 27.8, 22.8, 22.0, 18.8, 15.7; IR (thin film/NaCl) 3075 (w), 2979 (m), 2948 (m), 1743 (m), 1711 (s), 1637 (w), 1459 (m), 1434 (m), 1377 (w), 1278 (w), 1232 (m), 1212 (s), 1170 (w), 1133 (w), 1119 (w), 1004 (w), 915 (w), 753 (w) cm-1; HRMS (EI) m/z found: 264.1723 [calc'd for C16H24O3 (M+): 264.1725]. Second to elute was 6b (342 mg, 52% yield): 1H NMR (400 MHz, CDCl3) d 5.64 (ddt, J = 17, 10, 7.5 Hz, 1H), 5.03 (m, 2H), 3.67 (s, 3H), 2.67 (dd, J = 15, 8 Hz, 2H), 2.56 (dd, J = 14, 7.5 Hz, 1H), 2.24 (dd, J = 15, 9 Hz, 1H), 2.04 (td, J = 7, 5 Hz, 1H), 1.82 (dt, J = 15, 6.5 Hz, 1H), 1.42 (ddd, J = 15, 8.5, 5 Hz, 1H), 1.16 (d, J = 7 Hz, 3H), 1.05 (s, 3H), 0.99 (s, 3H), 0.80 (td, J = 9, 6.5 Hz, 1H), 0.63 (q, J = 9 Hz, 1H); 13C NMR (400 MHz, CDCl3) d 208.0, 171.9, 133.0, 118.3, 65.6, 51.4, 39.7, 37.6, 36.4, 28.5, 28.4, 22.9, 20.5, 20.2, 16.8, 15.0; IR (thin film/NaCl) 3076 (w), 2947 (m), 1738 (s), 1703 (s), 1639 (w), 1457 (m), 1434 (m), 1379 (w), 1268 (w), 1210 (s), 1148 (w), 1130 (w), 1078 (w) cm-1; HRMS (EI) m/z found: 264.1725 [calc'd for C16H24O3 (M+): 264.1725]. ______________________________________________________________________________ Preparation of enol ether 7.  EMBED ChemDraw.Document.4.5  To a sealed 50 ml round bottom flask containing KH powder (23 mg, 0.57 mmol, 1.5 equiv) was added a solution of 6a (102 mg, 0.38 mmol, 1.0 equiv) in DMF (10 mL). After stirring the mixture for 5 minutes, allyl bromide (100 uL, 1.0 mmol, 3.0 equiv) was injected into the reaction. The reaction was allowed to stir at room temperature for half an hour. Several drops of methanol were added into the reaction to quench excess KH. The crude product was diluted with ether and washed with NH4Cl and brine. After drying with MgSO4, the solvent was evaporated under reduced pressure. The yellow residue was purified by flash chromatography (50:1 Hexanes:EtOAc eluent). Enol ether 7 was collected as a light yellow oil (104 mg, 90% yield): 1H NMR (500 MHz, C6D6) d 6.15 (dtd, J = 17, 9, 5 Hz, 1H), 5.82 (ddt, J = 17, 11, 4.5 Hz, 1H), 5.37 (dq, J = 17, 2 Hz, 1H), 5.29 (m, 1H), 5.26 (m, 1H), 5.13 (qd, J = 11, 2 Hz, 1H), 4.90 (d, J = 2.5 Hz, 1H), 4.06 (m, 2H), 3.51 (s, 3H), 2.92 (dd, J = 14, 9 Hz, 1H), 3.36 (dtd, J = 15, 3.5, 1.5 Hz, 1H), 2.40 (ddd, J = 14, 9, 7 Hz, 1H), 2.30 (dt, J = 14, 5 Hz, 1H), 1.55 (dd, J = 14, 7 Hz, 1H), 1.30 (s, 3H), 1.18 (s, 3H), 1.07 (d, J = 7.0 Hz, 3H), 0.96-1.08 (m, 2H); 13C NMR (400 MHz, C6D6) d 174.3, 155.6, 136.2, 134.6, 118.0, 116.0, 101.4, 68.8, 62.1, 51.6, 39.7, 35.6, 31.2, 28.6, 28.4, 22.3, 20.7, 19.1, 16.6; IR (thin film/NaCl) 3075 (w), 2976 (m), 2947 (m), 1663 (w), 1646 (w), 1456 (w), 1433 (w), 1375 (w), 1295 (w), 1220 (s), 1185 (m), 1172 (m), 1138 (m), 1079 (w), 996 (w), 915 (w) cm-1; HRMS (EI) m/z found: 304.2037 [calc'd for C19H28O3 (M+): 304.2038]. ______________________________________________________________________________ Preparation of diene 8 via Claisen rearrangement.  EMBED ChemDraw.Document.4.5  In a 2 dram Fisher brand vial, enol ether 7 (104 mg, 0.34 mmol, 1.0 equiv) was dissolved in xylene (2 mL). The vial was stoppered and sealed with Teflon tape and heated in a 200C sand bath for 1 hour. The vial was removed from the sand bath and allowed to cool to room temperature. The yellow solution was purified by flash chromatography (40:1 Hexanes:EtOAc eluent). Diene 8 was collected as a light yellow oil (103 mg, 99% yield): 1H NMR (500 MHz, C6D6) d 6.41 (dddd, J = 17, 10.5, 9, 5.5 Hz, 1H), 5.89 (dddd, J = 17, 12.5, 7.5, 7.0 Hz, 1H), 5.04-5.24 (m, 4H), 3.35 (s, 3H), 3.23 (ddt, J = 14, 5.5, 1.5 Hz, 1H), 2.83 (dt, J = 13, 7 Hz, 1H), 2.65 (dd, J = 14, 9 Hz, 1H), 2.59 (dt, J = 10.5, 7 Hz, 1H), 2.48-2.54 (m, 1H), 2.15 (dt, J = 15.5, 11.5 Hz, 1H), 1.94 (dtd, J = 15, 7, 1.5 Hz, 1H), 1.75 (ddd, J = 15, 5.5, 1.5 Hz, 1H), 1.39 (d, J = 7 Hz, 3H), 1.08 (s, 3H), 1.01 (s, 3H), 0.56 (ddd, J = 12, 9, 6 Hz, 1H), 0.39 (dd, J = 10, 9 Hz, 1H); 13C NMR (400 MHz, C6D6) d 206.0, 172.1, 137.4, 136.5, 118.1, 116.5, 66.9, 51.7, 48.4, 39.7, 39.4, 36.9, 30.7, 29.3, 29.0, 27.5, 22.0, 18.7, 16.0; IR (thin film/NaCl) 3075 (w), 2978 (m), 2948 (m), 1744 (w), 1910 (s), 1639 (w), 1457 (w), 1434 (w), 1376 (w), 1216 (s), 1211 (w), 1029 (w), 913 (m) cm-1; HRMS (EI) m/z found: 304.2045 [calc'd for C19H28O3 (M+): 304.2038]. ______________________________________________________________________________ Preparation of RCM product 9.  EMBED ChemDraw.Document.4.5  To a solution of diene 8 (136 mg, 0.45 mmol, 1.0 equiv) in CH2Cl2 (60 mL) was added Grubbss catalyst (4) (37 mg, 0.05 mmol, 10 mol%). The reaction was heated to reflux for 24 hours. The crude solution was concentrated, and the residue was purified by flash chromatography (20:1 Hexanes:EtOAc eluent). The RCM product 9 was collected as a light pink oil (105 mg, 85% yield): 1H NMR (500 MHz, C6D6) d 5.80-5.91 (m, 2H), 2.58 (s, 3H), 3.21 (m, 1H), 3.13 (dd, J = 15.5, 7 Hz, 1H), 2.55 (dd, J = 16, 5.5 Hz, 1H), 2.39 (dqd, J = 17, 7, 2.5 Hz, 1H), 2.21-2.27 (m, 1H), 2.18 (dt, J = 16, 6 Hz, 1H), 1.78 (dt, J = 15.5, 10.5 Hz, 1H), 1.71 (ddd, J = 15.5, 7.5, 2 Hz, 1H), 1.07 (s, 3H), 1.06 (s, 3H), 1.01 (s, 3H), 0.58 (ddd, J = 11, 9, 7.5 Hz, 1H), 0.40 (dd, J = 9, 1.5 Hz, 1H); 13C NMR (400 MHz, C6D6) d 211.1, 173.2, 131.5, 130.0, 71.7, 54.4, 51.9, 37.2, 34.2, 33.5, 30.8, 29.9, 29.2, 27.2, 21.3, 18.3, 16.3; IR (thin film/NaCl) 3026 (w), 2949 (m), 1739 (s), 1682 (s), 1455 (m), 1376 (w), 1237 (m), 1181 (m), 1147 (w), 1046 (w), 998 (w), 808 (w), 779 (w), 686 (w) cm-1; HRMS (EI) m/z found: 276.1722 [calc'd for C17H24O3 (M+): 276.1725]. ______________________________________________________________________________ Preparation of diol 10.  EMBED ChemDraw.Document.4.5  To a solution of 9 (60 mg, 0.22 mmol, 1.0 equiv) in ether (10 mL) was added lithium aluminum hydride (12 mg, 0.44 mmol, 2.0 equiv). The mixture was allowed to stir at room temperature for 1 hour. Saturated Na2SO4 aqueous solution (0.5 mL) was carefully added into the solution to quench excess LAH. The mixture was kept stirring until the precipitates turned white. After adding MgSO4 to dry the solution, the product was filtered. The solvent was removed under reduced pressure. Diol 10 was collected as colorless crystals (50 mg, 95% yield): m.p. 146.5-148.7C; 1H NMR (500 MHz, CD2Cl2) d 5.53 (m, 2H), 4.04 (s, 1H), 3.64 (d, J = 4.0 Hz, 2H), 3.14-3.20 (m, 1H), 2.74 (s broad, 1H), 2.47-2.54 (m, 1H), 2.29 (s broad, 1H), 2.24-2.28 (m, 1H), 2.15 (m, 1H), 2.01 (dt, J = 14, 12 Hz, 1H), 1.74 (ddd, J = 14, 6, 4.5 Hz, 1H), 1.66 (m, 1H), 1.60 (dd, J = 16, 8 Hz, 1H), 1.12 (d, J = 7 Hz, 3H), 1.10 (s, 3H), 1.09 (s, 3H), 0.85 (ddd, J = 12, 9, 6 Hz, 1H), 0.55 (dd, J = 9.5, 4 Hz, 1H); 13C NMR (400 MHz, CD2Cl2) d 129.2, 125.3, 80.0, 71.5, 48.4, 41.0, 40.6, 39.0, 34.6, 31.0, 30.7, 28.9, 27.5, 20.8, 19.9, 15.9; IR (thin film/NaCl) 3428 (m), 3329 (s broad), 3011 (w), 2984 (m), 2949 (m), 2891 (s), 2860 (s), 1478 (w), 1452 (w), 1441 (w), 1373 (w), 1090 (w), 1048 (s), 1015 (m), 895 (w), 846 (w) cm-1; HRMS (EI) m/z found: 250.1934 [calc'd for C16H26O2 (M+): 250.1933]. ______________________________________________________________________________ Preparation of diene 3.  EMBED ChemDraw.Document.4.5  To a solution of 6b (125 mg, 0.47 mmol, 1.0 equiv) in dry THF (25 mL) was added KH powder (55 mg, 1.4 mmol, 3.0 equiv). The flask was then sealed under N2. Allyl bromide (150 uL, 1.5 mmol, 3.0 equiv) was injected into the solution. The reaction was allowed to reflux vigorously for 12 hours. The solution was cooled to room temperature, and carefully quenched with methanol (0.5 mL). The crude product was diluted with ether and washed with saturated NH4Cl and brine. After drying with MgSO4, the solvent was removed under reduced pressure. The residue was purified by flash chromatography (40:1 Hexanes:EtOAc eluent). Diene 3 was collected as a light yellow oil (121 mg, 85% yield): 1H NMR (500 MHz, C6D6) d 5.90 (dddd, J = 17, 10, 7.5, 7 Hz, 1H), 5.81 (ddt, J = 17, 10, 7.5 Hz, 1H), 5.07-5.21 (m, 4H), 3.52 (s, 3H), 2.89 (ddt, J = 14, 7.5, 1.5 Hz, 1H), 2.80 (ddt, J = 14, 8, 1.5 Hz, 1H), 2.69-2.76 (m, 1H), 2.57 (m, 1H), 2.43 (ddd, J = 10, 9, 5.5 Hz, 1H), 2.25 (m, 1H), 1.94 (ddd, J = 17, 10, 8 Hz, 1H), 1.60 (ddd, J = 17, 5.5, 4 Hz, 1H), 1.18 (d, J = 6.5 Hz, 3H), 1.03 (s, 3H), 0.95 (s, 3H), 0.78 (ddd, J = 9.5, 8.5, 5.5 Hz, 1H), 0.36 (t, J = 9.5 Hz, 1H); 13C NMR (400 MHz, C6D6) d 206.9, 172.2, 137.2, 133.5, 119.5, 117.0, 67.7, 51.9, 45.9, 40.3, 36.5, 35.0, 29.3, 29.1, 28.9, 23.6, 20.0, 17.2, 16.2; IR (thin film/NaCl) 3077 (w), 2978 (m), 2948 (m), 2865 (m), 1735 (s), 1705 (s), 1640 (w), 1435 (m), 1379 (w), 1262 (m), 1213 (s), 1155 (w), 995 (m), 915 (m) cm-1; HRMS (EI) m/z found: 304.2044 [calc'd for C19H28O3 (M+): 304.2038]. ______________________________________________________________________________ Preparation of ketal 17.  EMBED ChemDraw.Document.4.5  In a flame-dried 100 mL round bottom flask, CuCN (600 mg, 6.6 mmol, 1.4 equiv) was stirred with anhydrous ether (30 mL). The solution was chilled to 78C before adding MeLi (1.4 M, 4.7 mL, 6.6 mmol, 1.4 equiv). After the mixture was stirred for 30 minutes, a solution of 5 (998 mg, 4.7 mmol, 1.0 equiv) in ether (30 mL) was slowly added to the cuprate solution. The reaction was allowed to stir at 78C for 2 hours. After the reaction was warmed to room temperature, it was diluted with ether and washed with 10% NH4OH solution, water and brine. After drying with MgSO4, The solvent was evaporated under reduced pressure. The crude product was then dissolved in benzene (50 mL), followed by addition of ethylene glycol (1.3 ml, 23.5 mmol, 5.0 equiv) and catalytic PTSA (5 mg). The mixture was heated under Dean-Stark conditions for 12 hours. The crude solution was then washed with saturated NaHCO3 solution and brine. After drying with MgSO4, the solvent was removed. The residue was purified by flash chromatography (15:1:1 Hexanes:EtOAc:CH2Cl2 eluent). First to elute was 17c (186 mg, 15% yield): 1H NMR (500 MHz, C6D6) d 3.58-3.74 (m, 4H), 3.50 (s, 3H), 3.11 (s, 1H), 2.94 (dd, J = 14, 12 Hz, 1H), 2.48 (m, 1H), 2.35 (td, J = 11, 7.5 Hz, 1H), 2.12 (ddd, J = 15, 6, 2 Hz, 1H), 1.61 (dd, J = 15, 6 Hz, 1H), 1.41 (s, 3H), 1.19 (s, 3H), 1.08 (d, J = 7 Hz, 3H), 0.99 (m, 1H), 0.85 (ddd, J = 10.5, 9, 6.5 Hz, 1H); 13C NMR (400 MHz, C6D6) d 172.7, 111.5, 65.1, 64.7, 59.6, 51.2, 33.4, 31.2, 29.3, 28.1, 28.0, 22.5, 22.1, 20.8, 16.3; IR (thin film/NaCl) 2953 (m), 2932 (m), 2874 (m), 1732 (s), 1461 (w), 1368 (w), 1333 (w), 1308 (w), 1214 (m), 1148 (m), 1096 (m) cm-1; HRMS (EI) m/z found: 268.1672 [calc'd for C15H24O4 (M+): 268.1675]. Ketal 17b was eluted the second to deliver a colorless oil (165 mg, 13% yield): 1H NMR (500 MHz, C6D6) d 3.54-3.70 (m, 4H), 3.52 (s, 3H), 3.12 (dd, J = 3, 1.5 Hz, 1H), 2.82 (dd, J = 15, 11 Hz, 1H), 2.22-2.32 (m, 2H), 2.13 (ddd, J = 15, 6.5, 2 Hz, 1H), 1.78 (dt, J = 15, 6 Hz, 1H), 1.45 (d, J = 7 Hz, 3H), 1.35 (s, 3H), 1.17 (s, 3H), 0.88 (ddd, J = 10.5, 9, 6.5 Hz, 1H), 0.83 (ddt, J = 9.5, 5.5, 5.5 Hz, 1H); 13C NMR (400 MHz, C6D6) d 174.0, 112.7, 65.2, 64.5, 58.5, 51.6, 33.8, 32.4, 29.6, 26.3, 24.1, 21.6, 21.0, 20.0, 16.3; IR (thin film/NaCl) 2986 (m), 2951 (m), 2930 (m), 2875 (m), 1736 (s), 1459 (w), 1434 (w), 1378 (w), 1331 (w), 1306 (m), 1194 (m), 1173 (m), 1153 (m) cm-1; HRMS (EI) m/z found: 268.1675 [calc'd for C15H24O4 (M+): 268.1675]. Ketal 17 was eluted the third to furnish a white solid (444 mg, 35% yield): m.p. 92.6-94.7C; 1H NMR (500 MHz, C6D6) d 4.31 (q, J = 7.0 Hz, 1H), 3.86 (td, J = 7, 5 Hz, 1H), 3.77 (td, J = 7, 5 Hz, 1H), 3.59 (q, J = 7 Hz, 1H), 3.54 (s, 3H), 3.05 (d, J = 3.5 Hz, 1H), 2.40 (m, 1H), 2.06 (ddd, J = 14, 4, 2.5 Hz, 1H), 1.91 (dt, J = 14.5, 6 Hz, 1H), 1.63 (d, J = 7 Hz, 3H), 1.35-1.42 (m, 1H), 1.18-1.26 (m, 1H), 1.14 (s, 3H), 1.02 (s, 3H), 0.79-0.89 (m, 2H); 13C NMR (400 MHz, C6D6) d 172.2, 112.8, 66.9, 64.3, 60.6, 51.1, 36.4, 34.1, 31.4, 29.6, 24.3, 21.8, 20.1, 16.0, 15.2; IR (thin film/NaCl) 2952 (s), 2932 (s), 2875 (s), 1739 (s), 1455 (m), 1434 (m), 1379 (m), 1352 (w), 1310 (w), 1271 (w), 1195 (m), 1179 (m), 1131 (m) cm-1; HRMS (EI) m/z found: 268.1675 [calc'd for C15H24O4 (M+): 268.1675]. The last to elute was 17d (237 mg, 19% yield), which furnished a white solid: m.p. 53.2-54.0C; 1H NMR (500 MHz, C6D6) d 4.02 (m, 1H), 3.72 (m, 2H), 3.57-3.62 (m, 1H), 3.58 (s, 3H), 2.58-2.69 (m, 2H), 2.09 (dd, J = 14, 6 Hz, 1H), 1.73 (dd, J = 15, 6 Hz, 1H), 1.46 (dd, J = 14.5 Hz, 1H), 1.13 (s, 3H), 1.04 (d, J = 7 Hz, 3H), 1.02 (s, 3H), 0.97 (m, 1H), 0.89 (ddd, J = 11, 9, 6.5 Hz, 1H), 0.81 (ddd, J = 11, 9, 6.5 Hz, 1H); 13C NMR (400 MHz, C6D6) d 173.0, 111.7, 66.2, 65.1, 64.8, 51.3, 35.9, 34.5, 33.4, 29.5, 27.5, 22.72, 22.68, 20.2, 16.1; IR (thin film/NaCl) 2953 (m), 1740 (s), 1460 (w), 1434 (w), 1353 (w), 1271 (w), 1208 (w), 1168 (w), 1140 (m), 1044 (m), 984 (w), 948 (w), 801 (w) cm-1; HRMS (EI) m/z found: 268.1674 [calc'd for C15H24O4 (M+): 268.1675]. ______________________________________________________________________________ Preparation of alcohol 18.  EMBED ChemDraw.Document.4.5  To a solution of 17 (1.2 g, 4.5 mmol, 1.0 equiv) in anhydrous ether (100 mL) was added lithium aluminum hydride (342 mg, 9.0 mmol, 2.0 equiv). The mixture was allowed to stir under N2 for two hours. Saturated Na2SO4 solution was carefully added into the solution to quench excess LAH. The mixture was kept stirring until the precipitates turned white. After adding MgSO4 to dry the solution, the product was filtered. The solvent was removed under reduced pressure. The crude oil was dissolved in acetone (20 mL), followed by addition of 1 M HCl (1.0 mL). The solution was allowed to stir at room temperature for 30 minutes. Saturated sodium bicarbonate solution (5 mL) was added to neutralize the acid. Organic solvent was removed under reduced pressure. The aqueous phase was extracted with ether, and the extraction was washed with brine. After drying with MgSO4, the solution was concentrated under reduced pressure. The crude product was purified by flash chromatography (3:1 Hexane:EtOAc eluent). Alcohol 18 was collected as a colorless oil (0.84 g, 95% 2 steps): 1H NMR (500 MHz, C6D6) d 4.23 (t, J = 10 Hz, 1H), 3.58 (m, 1H), 2.55 (dd, J = 11.5, 6.5 Hz, 1H), 2.48 (dt, J = 8, 4.5 Hz, 1H), 2.19 (s broad, 1H), 2.00 (m, 1H), 1.83 (m, 2H), 1.13 (ddd, J = 15, 11, 1.5 Hz, 1H), 1.00 (s, 3H), 0.94 (s, 3H), 0.88 (d, J = 7.0 Hz, 3H), 0.51-0.61 (m, 2H); 13C NMR (400 MHz, C6D6) d 209.6, 62.54, 62.50, 41.2, 32.9, 30.9, 29.1, 24.2, 21.2, 20.8, 15.6, 14.0; IR (thin film/NaCl) 3430 (m broad), 2935 (s), 2877 (s), 1698 (s), 1455 (m), 1382 (m), 1289 (w), 1202 (w), 1155 (w), 1117 (w), 1025 (m), 984 (w), 940 (w) cm-1; HRMS (EI) m/z found: 196.1457 [calc'd for C12H20O2 (M+): 196.1463]. ______________________________________________________________________________ Preparation of acetal 19.  EMBED ChemDraw.Document.4.5  To a solution of alcohol 18 (450 mg, 2.3 mmol, 1.0 equiv) in pyridine (10 mL) was sequentially added acetic anhydride (1.1 mL, 12 mmol, 5.0 equiv) and catalytic DMAP (2 mg). The mixture was allowed to stir at room temperature for half an hour. Pyridine was removed from the reaction under reduced pressure. The yellow colored residue was purified by flash chromatography (20:1 Hexanes:EtOAc eluent). A colorless oil 19 was collected (526 mg, 96% yield): 1H NMR (500 MHz, C6D6) d 4.82 (dd, J = 11, 8 Hz, 1H), 4.29 (dd, J = 11, 6 Hz, 1H), 2.62 (ddd, J = 7.5, 6, 4.5 Hz, 1H), 2.51 (m, 1H), 2.05 (m, 1H), 1.83 (s, 3H), 1.80 (m, 2H), 1.10 (ddd, J = 15, 11, 1.5 Hz, 1H), 0.99 (s, 3H), 0.92 (s, 3H), 0.85 (d, J = 6.5 Hz, 3H), 0.54 (m, 2H); 13C NMR (400 MHz, C6D6) d 206.1, 170.7, 63.9, 58.6, 40.8, 32.8, 30.6, 29.1, 24.0, 21.2, 21.1, 21.0, 15.6, 13.4; IR (thin film/NaCl) 2937 (m), 1742 (s), 1703 (s), 1456 (m), 1368 (m), 1240 (s), 1203 (m), 1152 (w), 1031 (m), 983 (w) cm-1; HRMS (EI) m/z found: 238.1563 [calc'd for C14H22O3 (M+): 238.1569]. ______________________________________________________________________________ Preparation of exo-olefin 14. EMBED ChemDraw.Document.4.5 To a solution of 19 (500 mg, 2.1 mmol 1.0 equiv) in benzene (150 mL), was added DBU (947 uL, 6.3 mmol, 3.0 equiv). The mixture was heated to reflux for 10 hours. After cooling to room temperature, the crude product was washed with saturated NH4Cl solution, brine, and then dried over anhydrous MgSO4. Concentration under reduced pressure afforded a yellow oil, which was purified by flash chromatography (60:1 Hexanes:Et2O eluent). A colorless oil was collected as exo-olefin 14 (332 mg, 88% yield): 1H NMR (500 MHz, C6D6) d 6.07 (dd, J = 2.0, 0.5 Hz, 1H), 5.06 (dd, J = 2.0, 1.0 Hz, 1H), 2.69 (dd, J = 13, 7.0 Hz, 1H), 2.33 (h, J = 7.0 Hz, 1H), 2.18 (dd, J = 13, 11 Hz, 1H), 1.63 (m, 2H), 1.04 (d, J = 7.0 Hz, 3H), 0.97 (s, 3H), 0.86 (s, 3H), 0.66 (ddd, J = 11, 9.0, 7.0 Hz, 1H), 0.57 (td, J = 9.0, 7.0 Hz, 1H); 13C NMR (400 MHz, C6D6) d 201.8, 155.0, 118.3, 38.3, 36.3, 32.5, 31.0, 29.0, 22.7, 20.5, 19.3, 15.3; IR (thin film/NaCl) 2959 (s), 1697 (s), 1608 (m), 1457 (m), 1377 (w), 1266 (m), 1138 (w), 940 (w), 770 (w) cm-1; HRMS (EI) m/z found: 178.1359 [calc'd for C17H24O (M+): 178.1358]. ______________________________________________________________________________ Preparation of Diels-Alder product 20a. EMBED ChemDraw.Document.4.5 In a flame-dried 100 mL round bottom flask, exo-olefin 14 (400 mg, 2.25 mmol, 1.0 equiv) was dissolved in toluene (25 mL). After the solution was chilled to 78C in a dry ice bath, boron trifluoride diethyl etherate (556 uL, 4.50 mmol, 2.0 equiv) was added into the flask. The mixture was allowed to stir at 78C for 15 minutes before adding newly cracked cyclopentadiene monomer (15) (1.85 mL, 22.5 mmol, 10 equiv). The reaction mixture was allowed to stir at -78C under N2 for one hour. Water (2 mL) was injected into the flask to quench the reaction. The reaction was allowed to warm to room temperature slowly. The reaction mixture was diluted with ether, and the crude product was washed with 1 M NaOH, water and brine. After drying with MgSO4, the solvent was evaporated under reduced pressure. The residue was purified by flash chromatography (150:1 hexanes: Et2O eluent). First to elute was product 20b to furnish a light yellow solid (130 mg, 24% yield): m.p. 63.5-66.2C; 1H NMR (500 MHz, C6D6) d 6.22 (dd, J = 5.8, 3.0 Hz, 1H), 5.97 (dd, J = 5.0, 3.0 Hz, 1H), 3.18 (dd, J = 12, 4 Hz, 1H), 2.94 (d, J = 1.5 Hz, 1H), 2.72 (s, 1H), 2.62 (dd, J = 12, 7.0 Hz, 1H), 2.48 (dd, J = 7.0, 5.0 Hz, 1H), 1.79 (dt, J = 15, 6.0 Hz, 1H), 1.55 (m, 1H), 1.46 (m, 2H), 1.20 (d, J = 8.0 Hz, 1H), 1.08 (s, 3H), 1.06 (s, 3H), 1.01 (d, J = 6.5 Hz, 3H), 0.77 (dd, J = 12, 2.5 Hz, 1H), 0.70 (m, 2H); 13C NMR (400 MHz, C6D6) d 208.9, 141.3, 133.4, 67.9, 50.1, 48.4, 42.8, 40.4, 36.7, 33.5, 29.2, 27.1, 24.9, 21.9, 21.2, 16.2, 15.9; IR (thin film/NaCl) 3058 (w), 2944 (s), 2875 (m), 1693 (s), 1457 (m), 1380 (m), 1301 (w), 1240 (w), 1206 (w), 1191 (w), 1148 (w), 982 (w), 778 (w), 721 (m), 644 (w) cm-1; HRMS (EI) m/z found: 244.1826 [calc'd for C17H24O (M+): 244.1827]. Product 20c was eluted the second to furnish a colorless oil (16 mg, 3.0% yield): 1H NMR (500 MHz, C6D6) d 6.70 (dd, J = 5.5, 3.0 Hz, 1H), 6.10 (dd, J = 5.5, 3.0 Hz, 1H), 3.40 (q, J = 1.5 Hz, 1H), 2.70 (s, 1H), 2.35 (dd, J = 11.8, 6.8 Hz, 1H), 2.10 (t, J = 11 Hz, 1H), 1.80 (m, 2H), 1.50 (m, 3H), 1.40 (m, 1H), 1.32 (d, J = 12 Hz, 1H), 1.12 (d, J = 6.5 Hz, 3H), 1.04 (s, 3H), 1.02 (s, 3H), 0.75 (ddd, J = 11, 10.5, 6.5 Hz, 1H), 0.66 (m, 1H); 13C NMR (400 MHz, C6D6) d 209.2, 140.8, 136.4, 68.3, 46.9, 46.3, 42.8, 41.6, 38.6, 37.7, 29.2, 28.0, 23.6, 22.5, 21.8, 15.8, 14.9; IR (thin film/NaCl) 3058 (w), 2959 (s), 2875 (s), 1694 (s), 1455 (m), 1379 (w), 1332 (w), 1253 (w), 1148 (w), 781 (w), 717 (m), 646 (m), 589 (m) cm-1; HRMS (EI) m/z found: 244.1825 [calc'd for C17H24O (M+): 244.1827]. Third to elute was product 20a (326 mg, 59% yield): m.p. 62.1-64.2C; 1H NMR (500 MHz, C6D6) d 6.19 (dd, J = 5.5, 3.0 Hz, 1H), 5.93 (dd, J = 5.5, 3.0 Hz, 1H), 2.82 (s, 1H), 2.72 (s, 1H), 2.66 (dd, J = 12, 3.0 Hz, 1H), 2.49 (dd, J = 12, 7.0 Hz, 1H), 2.18 (t, J = 11 Hz, 1H), 1.80 (m, 1H), 1.76 (m, 2H), 1.59 (dd, J = 14, 11 Hz, 1H), 1.48 (m, 1H), 1.44 (d, J = 8.5 Hz, 1H), 1.36 (dd, J = 12, 4.0 Hz, 1H), 1.10 (d, J = 7.0 Hz, 3H), 1.08 (s, 3H), 1.06 (s, 3H), 0.70 (m, 2H); 13C NMR (400 MHz, C6D6) d 206.8, 140.5, 133.9, 67.2, 48.9, 48.2, 43.8, 40.4, 38.1, 35.9, 29.2, 27.4, 24.2, 21.59, 21.56, 16.5, 16.1; IR (thin film/NaCl) 3056 (w), 2971 (s), 2877 (m), 1700 (s), 1457 (w), 1380 (w), 1336 (w), 1277 (w), 779 (w), 710 (m), 647 (w) cm-1; HRMS (EI) m/z found: 244.1827 [calc'd for C17H24O (M+): 244.1827]. ______________________________________________________________________________ Preparation of 13.  EMBED ChemDraw.Document.4.5  To a 25ml round bottom flask containing a solution of 20a (25 mg, 0.10 mmol, 1.0 equiv) in THF (10 mL) was sequentially added KH powder (20 mg, 0.50 mmol, 5.0 equiv) and allyl bromide (100 uL, 1.0 mmol, 10 equiv). The reaction was allowed to reflux vigorously for 12 hours. After the solution was cooled to room temperature, methanol (0.5 mL) was carefully added to quench excess KH. The crude product was diluted with ether. The solution was then washed with saturated NH4Cl and brine. After drying with MgSO4, the crude product was concentrated. The residue was purified by flash chromatography. Compound 13 was collected as a white solid (22 mg, 76% yield): m.p. 61.2-62.9C; 1H NMR (500 MHz, CDCl3) d 6.15 (dd, J = 6, 3 Hz, 1H), 5.94 (dd, J = 6, 3 Hz, 1H), 5.75 (ddt, J = 17, 10, 7.5 Hz, 1H), 5.00-5.09 (m, 2H), 2.99 (s, 1H), 2.78 (s, 1H), 2.37 (m, 1H), 2.26 (td, J = 10, 4 Hz, 1H), 2.18 (m, 2H), 1.90 (m, 2H), 1.63 (m, 1H), 1.57 (d, J = 8.5 Hz, 1H), 1.42-1.46 (m, 1H), 1.40 (dd, J = 12, 4 Hz, 1H), 1.060 (s, 3H), 1.058 (s, 3H), 0.94 (d, J = 7 Hz, 3H), 0.70 (ddd, J = 11, 9, 6 Hz, 1H), 0.15 (t, J = 9 Hz, 1H); 13C NMR (400 MHz, CDCl3) d 210.2, 139.9, 136.7, 133.1, 115.9, 66.4, 47.9, 47.4, 46.6, 42.8, 40.1, 36.1, 35.6, 28.8, 27.1, 26.7, 23.3, 21.0, 16.0, 15.6; IR (thin film/NaCl) 3063 (w), 2975 (s), 2878 (m), 1699 (s), 1640 (w), 1445 (w), 1381 (w), 1261 (w), 1088 (w), 994 (w), 909 (m), 864 (w), 712 (m), 680 (w) cm-1; HRMS (EI) m/z found: 284.2140 [calc'd for C20H28O (M+): 284.2140]. ______________________________________________________________________________ Preparation of triene 12 via ROM.  EMBED ChemDraw.Document.4.5  To a solution of 13 (56 mg, 0.20 mmol, 1.0 equiv) in CH2Cl2 (50 mL) was added catalyst 4 (5.0 mg, 0.006 mmol, 3 mol%). The reaction was allowed to stir under ethylene gas for 6 hours. Concentration under reduced pressure with concomitant adsorption onto silica gel was followed by flash chromatography (40:1 Hexanes:Et2O eluent). A light pink oil was collected as triene 12 (59 mg, 95% yield): 1H NMR (500 MHz, CDCl3) d 5.82 (ddd, J = 17, 10, 7.5 Hz, 1H), 5.69 (ddt, J = 17, 10, 7 Hz, 1H), 5.59 (dt, J = 17, 10 Hz, 1H), 4.94-5.03 (m, 5H), 4.90 (dt, J = 10, 1.5 Hz, 1H), 2.75 (m, 1H), 2.54 (m, 1H), 2.20-2.37 (m, 3H), 2.16 (t, J = 9 Hz, 1H), 2.01 (dd, J = 14, 7 Hz, 1H), 1.95 (ddd, J = 14, 7, 2 Hz, 1H), 1.83 (m, 2H), 1.63 (ddd, J = 15, 10, 2 Hz, 1H), 1.36 (ddd, J = 13, 8, 4 Hz, 1H), 1.03 (s, 3H), 1.00 (s, 3H), 0.94 (d, J = 7 Hz, 3H), 0.69 (td, J = 9, 7 Hz, 1H), 0.15 (t, J = 9.5 Hz, 1H); 13C NMR (400 MHz, CDCl3) d 212.1, 143.2, 140.9, 136.7, 115.6, 115.1, 112.7, 68.1, 50.1, 47.1, 39.8, 38.0, 35.9, 35.6, 34.9, 28.7, 27.4, 27.0, 22.7, 20.8, 15.9, 14.8; IR (thin film/NaCl) 3075 (m), 2977 (s), 2954 (s), 2864 (m), 1694 (s), 1640 (w), 1453 (m), 1419 (w), 1378 (w), 1264 (w), 1164 (w), 996 (m), 909 (s) cm-1; HRMS (EI) m/z found: 312.2444 [calc'd for C22H32O (M+): 312.2453]. ______________________________________________________________________________ Reversion to 13 via RCM.  EMBED ChemDraw.Document.4.5  A solution of 12 (40 mg, 0.06 mmol, 1.0 equiv) in toluene (40 mL) was heated to reflux for 3 hours. During this time, three portions of catalyst 4 (20 mg, 0.0024 mmol, 20 mol%) was added to the reaction every 60 minutes. Toluene was removed under reduced pressure. The crude product was purified by flash chromatography (30:1 Hexanes:Et2O eluent). A light pink solid was collected as compound 22 (2.6 mg, 8% yield). (Experimental data identical to the alkylation product) ______________________________________________________________________________ Preparation of diene 22.  EMBED ChemDraw.Document.4.5  To a solution of 20a (250 mg, 1.0 mmol, 1.0 equiv) in dichloromethane (150 mL) was added 4 (16 mg, 0.020 mmol, 2.0 mol%). The solution was allowed to stir at room temperature under ethylene gas for 12 hours. Concentration under reduced pressure with concomitant adsorption onto silica gel was followed by flash chromatography (40:1 Hexanes:Et2O eluent). Diene 22 was collected to furnish a white solid (266 mg, 98% yield): m.p.64.5-65.5C; 1H NMR (500 MHz, C6D6) d 5.94 (ddd, J = 17, 10, 7.5 Hz, 1H), 5.69 (dt, J = 17, 10 Hz, 1H), 5.16 (ddd, J = 17, 2, 1 Hz, 1H), 5.06 (ddd, J = 10, 2, 1 Hz, 1H), 4.96 (ddd, J = 17, 2, 0.5 Hz, 1H), 4.91 (dd, J = 10, 2 Hz, 1H), 2.48-2.61 (m, 3H), 2.32 (dd, J = 12, 11 Hz, 1H), 2.20-2.27 (m, 2H), 2.16 (ddd, J = 13, 9, 8 Hz, 1H), 1.69-1.81 (m, 2H), 1.59 (ddd, J = 14.5, 9.5, 1.5 Hz, 1H), 1.50 (ddd, J = 14, 7.5, 4 Hz, 1H), 1.07 (s, 3H), 1.03 (s, 3H), 0.96 (d, J = 7 Hz, 3H), 0.70 (ddd, J = 10.5, 9, 6.5 Hz, 1H), 0.65 (td, J = 9, 6 Hz, 1H); 13C NMR (400 MHz, C6D6) d 209.1, 144.2, 141.9, 115.4, 113.5, 69.2, 50.9, 40.9, 39.6, 38.8, 36.9, 35.5, 29.1, 27.3, 23.5, 21.7, 21.4, 15.8, 15.5; IR (thin film/NaCl) 3076 (w), 2975 (m), 2944 (m), 1696 (s), 1639 (w), 1457 (w), 1420 (w), 1378 (w), 1297 (w), 1272 (w), 1203 (w), 996 (m), 911 (m), 643 (w) cm-1; HRMS (EI) m/z found: 272.2140 [calc'd for C19H28O (M+): 272.2140]. ______________________________________________________________________________ Preparation of acetal 23.  EMBED ChemDraw.Document.4.5  To a solution of diene 22 (794 mg, 3.0 mmol, 1.0 equiv) in THF/H2O (4:1, 25 mL) was added 2.5 wt. % OsO4 solution in 2-methyl-2-propanol (940 uL, 0.08 mmol, 2.5 mol%) and NMO (386 mg, 3.3 mmol, 1.1 equiv). The mixture was allowed to stir at room temperature for 8 hours. The crude solution was diluted with ether. After washing with NaHCO3 and brine, the solution was filtered through a silica gel pad. After drying with MgSO4, the solvent was evaporated under reduced pressure. The residue was then dissolved in a solvent mixture of CH3OH/THF (4:1, 30 mL), followed by addition of an aqueous solution of 0.5 M NaIO4 (18 mL, 9.0 mmol, 3.0 equiv). The mixture was allowed to stir at room temperature for 1 hour. The reaction was diluted with water (20 mL), and the crude product was extracted with ether. After drying with MgSO4, the solvent was rotavapored and the resultant colorless oil was then dissolved in benzene (30 mL). To this solution was added ethylene glycol (0.85 mL, 15 mmol, 5.0 equiv) and catalytic PPTS (5 mg). The reaction was heated to reflux for 4 hours under Dean-Stark conditions. After the solution was cooled to room temperature, the crude product was diluted with ether. The crude solution was washed with NaHCO3 and brine, and then dried over MgSO4. The solvent was removed under reduced pressure. The residue was purified by flash chromatography (10:1 Hexanes:EtOAc eluent). A colorless oil was collected as acetal 23 (696 mg, 73% yield over 3 steps): 1H NMR (500 MHz, C6D6) d 5.91 (dt, J = 17, 10 Hz, 1H), 4.98 (dd, J = 17, 2 Hz, 1H), 4.94 (dd, J = 10, 2 Hz, 1H), 4.89 (d, J = 5 Hz, 1H), 3.68 (m, 2H), 3.52 (m, 2H), 2.62 (td, J = 9, 2.5 Hz, 1H), 2.57 (dd, J = 12, 6.5 Hz, 1H), 2.34-2.48 (m, 3H), 2.29 (dd, J = 12, 11 Hz, 1H), 2.22 (m, 1H), 1.72-1.82 (m, 2H), 1.70 (dt, J = 15, 6 Hz, 1H), 1.57 (ddd, J = 15, 10, 1 Hz, 1H), 1.06 (s, 3H), 1.02 (s, 3H), 0.98 (d, J = 7 Hz, 3H), 0.67 (m, 2H); 13C NMR (400 MHz, C6D6) d 209.0, 141.9, 115.2, 107.9, 69.5, 65.7, 65.6, 50.3, 40.2, 39.7, 35.2, 33.0, 31.8, 29.1, 26.9, 23.7, 21.6, 15.9, 15.3; IR (thin film/NaCl) 3073 (w), 2953 (m), 1696 (s), 1457 (w), 1380 (w), 1272 (w), 1156 (m), 1096 (m), 1077 (m), 995 (w), 940 (w), 913 (w) cm-1; HRMS (EI) m/z found: 318.2191 [calc'd for C20H30O3 (M+): 318.2195]. ______________________________________________________________________________ Preparation of RCM precursor 24.  EMBED ChemDraw.Document.4.5  To a solution of acetal 23 (580 mg, 1.8 mmol, 1.0 equiv) in dry THF (40 mL) was sequentially added KH powder (365 mg, 9.1 mmol, 5.0 equiv) and allyl bromide (2.0 ml, 18.2 mmol, 10 equiv). The reaction was heated to reflux vigorously for 10 hours. After cooling to room temperature, methanol was carefully added into the reaction to quench excess KH. The crude product was extracted with ether, and the solution was washed with NH4Cl and brine. After drying with MgSO4, the solvent was removed, and the yellow residue was purified by silica gel chromatography (30:1 Hexanes:EtOAc eluent). Diene 24 was collected to furnish a white solid (592 mg, 92% yield): m.p. 64.1-65.1C; 1H NMR (500 MHz, C6D6) d 5.63 (ddd, J = 17, 10, 7.5 Hz, 1H), 5.62 (ddd, J = 17, 10.5, 10 Hz, 1H), 4.91 (dd, J = 17, 2 Hz, 1H), 4.85 (dd, J = 10, 2 Hz, 1H), 4.70 (dd, J = 17, 2.5 Hz, 1H), 4.67 (dd, J = 10, 2.5 Hz, 1H), 4.62 (d, J = 3 Hz, 1H), 3.41 (m, 2H), 3.24 (m, 2H), 2.51 (ddd, J = 13, 10, 8 Hz, 1H), 2.38 (m, 1H), 2.25 (ddd, J = 12.5, 7.5, 4 Hz, 1H), 2.11 (m, 4H), 1.95 (m, 1H), 1.40-1.50 (m, 3H), 1.28 (dd, J = 14, 11 Hz, 1H), 0.81 (s, 3H), 0.80 (s, 3H), 0.71 (d, J = 6.5 Hz, 3H), 0.41 (td, J = 10, 6 Hz, 1H), 0.00 (dd, J = 10, 9 Hz, 1H); 13C NMR (400 MHz, C6D6) d 210.6, 142.1, 137.9, 116.2, 115.2, 107.8, 69.3, 65.7, 65.6, 50.1, 48.1, 39.9, 37.0, 35.2, 33.0, 32.1, 29.3, 27.9, 27.1, 23.6, 21.6, 16.8, 15.2; IR (thin film/NaCl) 3073 (w), 2975 (s), 2880 (s), 1694 (s), 1639 (w), 1454 (m), 1415 (w), 1379 (w), 1156 (m), 1094 (m), 1034 (m), 996 (m), 911 (m), 752 (w), 651 (w) cm-1; HRMS (EI) m/z found: 358.2503 [calc'd for C23H34O3 (M+): 358.2508]. ______________________________________________________________________________ Preparation of 25 using RCM.  EMBED ChemDraw.Document.4.5  A solution of 24 (50 mg, 0.14 mmol, 1.0 equiv) in dry toluene (50 mL) was heated to reflux for 3 hours. During this time, four portions of catalyst 4 (23 mg, 0.028 mmol, 20 mol%) were added to the solution every 45 minutes. After cooling to room temperature, Pb(OAc)4 (101 mg, 0.28 mmol, 2.0 equiv), and the mixture was allowed to stir for 24 hours. The crude solution was poured on a short silica gel column (15:1 Hexanes:Et2O eluent), and the product was collected as a pink oil. The RCM product was further purified by HPLC (20:1 Hexanes:Et2O eluent). The purified product was a colorless oil 25 (21 mg, 45% yield): 1H NMR (500 MHz, 80C, C6D6) d 5.50 (m, 2H), 4.82 (d, J = 5 Hz, 1H), 3.70 (m, 2H), 3.55 (m, 2H), 3.29 (td, J = 13, 3.5 Hz, 1H), 3.06 (d, J = 3.5 Hz, 1H), 2.66 (m, 1H), 2.10-2.45 (m, 5H), 1.90 (m, 1H), 1.76 (dd, J = 7.5, 4.5 Hz, 2H), 1.70 (ddd, J = 12.5, 7, 4.5 Hz, 1H), 1.13 (s, 3H), 1.05 (d, J = 7 Hz, 3H), 1.04 (s, 3H), 0.91 (dd, J = 12, 9 Hz, 1H), 0.70 (q, J = 8 Hz, 1H); 13C NMR (400 MHz, 80C, C6D6) d 210.5, 138.4, 131.2, 108.0, 72.4, 66.7, 46.3, 46.1, 43.3, 37.5, 35.9, 32.6, 31.2, 30.3, 29.8, 29.3, 25.1, 24.7, 23.5, 16.3, 15.7; IR (thin film/NaCl) 2999 (m), 2948 (m), 2876 (m), 1721 (s), 1457 (w), 1380 (w), 1160 (w), 1103 (w), 1036 (w), 960 (w) cm-1; HRMS (EI) m/z found: 330.2187 [calc'd for C21H30O3 (M+ 330.2195]. ______________________________________________________________________________ Preparation of diol 26.  EMBED ChemDraw.Document.4.5  To a solution of RCM product 25 (66 mg, 0.20 mg, 1.0 equiv) in THF/H2O (4:1 15 mL) was added 2.5 wt. % OsO4 solution in 2-methyl-2-propanol (50 uL, 0.004 mmol, 2 mol%) and NMO (117 mg, 1.0 mmol, 5.0 equiv). The mixture was allowed to stir at room temperature for 12 hours. The crude product was extracted with ether. The solution was washed with brine. After drying over MgSO4, solvent was removed under reduced pressure. The residue was purified with flash chromatography (2:1 Hexanes:EtOAc eluent). After evaporation of solvent, diol 26 was collected as a colorless oil (60 mg, 82% yield): 1H NMR (500 MHz, 80C, C6D6) d 4.82 (d, J = 4 Hz, 1H), 4.00 (s broad, 1H), 3.70 (m, 2H), 3.55 (m, 2H), 3.34 (d, J = 8 Hz, 1H), 3.25 (td, J = 14, 2 Hz, 1H), 2.66 (q, J = 7 Hz, 1H), 2.43 (m, 1H), 2.35 (broad, 1H), 2.20 (m, 2H), 2.14 (td, J = 6.5, 2.5 Hz, 1H), 2.08 (dd, J = 14, 7 Hz, 1H), 1.97 (t, J = 7.5 Hz, 2H), 1.87 (ddd, J = 13, 7.5, 2.5 Hz, 1H), 1.78 (m, 2H), 1.50 (broad, 1H), 1.32 (s, 3H), 1.06 (s, 3H), 1.03 (d, J = 7 Hz, 3H), 0.90 (dd, J = 11.5, 8.5 Hz, 1H), 0.67 (q, J = 8.5 Hz, 1H); 13C NMR (400 MHz, 80C, C6D6) d 212.4, 107.9, 77.4, 75.2, 68.8, 65.8, 65.6, 47.9, 42.4, 42.2, 37.6, 34.0, 30.9, 29.6, 28.1, 27.9, 25.8, 25.2, 23.7, 17.0, 15.4; IR (thin film/NaCl) 3454 (m broad), 2926 (s), 2883 (s), 1713 (s), 1453 (w), 1220 (w), 1159 (w), 1034 (m), 940 (w) cm-1; HRMS (EI) m/z found: 364.2248 [calc'd for C21H32O5 (M+): 364.2250]. ______________________________________________________________________________ Preparation of dibenzoate 27.  EMBED ChemDraw.Document.4.5  To a solution of diol 26 (30 mg, 0.08 mmol, 1.0 equiv) in dichloromethane (10 mL) was sequentially added para-bromobenzoic chloride (88 mg, 0.40 mmol, 5.0 equiv) and DMAP (25 mg, 0.20 mmol, 2.5 equiv). The flask was then sealed under N2. Triethyl amine (110 uL, 0.80 mmol, 10 equiv) was injected into the reaction. The reaction was allowed to stir at room temperature for 8 hours. Concentration under reduced pressure with concomitant adsorption onto silica gel was followed by flash chromatography (4:1 Hexanes:EtOAc eluent). A crystalline solid was collected as diester 27 (51 mg, 84% yield): m.p. 183.6-184.8C; 1H NMR (500 MHz, 80C, C6D6) d 7.88 (dd, J = 8.5, 7 Hz, 4H), 7.34 (m, 4H), 5.88 (t, J = 4.5 Hz, 1H), 5.69 (s broad, 1H), 4.77 (d, J = 5.5 Hz, 1H), 3.67 (m, 2H), 3.59 (t, J = 10 Hz, 1H), 3.51 (m, 2H), 2.89 (d, J = 6 Hz, 1H), 2.70 (t, J = 13 Hz, 1H), 2.56 (dt, J = 13, 5 Hz, 1H), 2.37 (m, 1H), 2.31 (m, 1H), 2.21 (dt, J = 14, J = 7 Hz, 1H), 1.85-2.00 (m, 4H), 1.75 (ddd, J = 16, 9, 7 Hz, 1H), 1.50 (broad, 1H), 1.23 (s, 3H), 1.02 (s, 3H), 0.96 (d, J = 7 Hz, 3H), 0.65 (ddd, J = 8.5, 6.5, 4.5 Hz, 1H); 13C NMR (400 MHz, 80C, C6D6) d 210.4, 165.4, 165.2, 132.6, 131.9, 131.8, 130.4, 130.3, 107.6, 79.3, 74.8, 68.1, 65.7, 50.1, 43.3, 41.5, 41.3, 39.6, 32.1, 31.4, 31.0, 29.4, 27.1, 26.5, 25.4, 22.9, 17.1, 15.8; IR (thin film/NaCl) 2955 (w), 2883 (w), 1723 (s), 1590 (m), 1484 (w), 1398 (w), 1272 (s), 1173 (w), 1113 (m), 1100 (m), 1012 (m), 923 (w), 847 (w), 754 (m), 737 (w), 682 (w) cm-1; HRMS (EI) m/z found: 730.0952 [calc'd for C35H38 Br2O7 (M+): 730.0964]. X-RAY CRYSTALLOGRAPHY REPORT FOR DIOL 10  EMBED ChemDraw.Document.4.5  Data Collection A colorless plate crystal of CADVANCE \d332ADVANCE \u3HADVANCE \d352ADVANCE \u3OADVANCE \d34ADVANCE \u3 having approximate dimensions of 0.05 x 0.12 x 0.19 mm was mounted on a glass fiber. All measurements were made on a Nonius KappaCCD diffractometer with graphite monochromated Mo-K radiation. Cell constants and an orientation matrix for data collection, obtained from a least-squares refinement using ten (1o in , 10s exposure, de-zingered) data frames, corresponded to a primitive monoclinic cell with dimensions: a = 9.7381(2) , b = 13.3319(4) ,  = 101.424(2)ADVANCE \u3oADVANCE \d3, c = 11.5709(3) , and V = 1472.46(6) ADVANCE \u33ADVANCE \d3. For Z = 2 and F.W. = 500.76, the calculated density is 1.13 g/cmADVANCE \u33ADVANCE \d3. Based on the systematic absences of: 0k0: k = 2n+1; packing considerations, a statistical analysis of intensity distribution, and the successful solution and refinement of the structure, the space group was determined to be: P2ADVANCE \d31ADVANCE \u3 (#4). There are two independent, but essentially identical, molecules per asymmetric unit. The data were collected at a temperature of -90 + 1ADVANCE \u3oADVANCE \d3C to a maximum 2 value of 50.0ADVANCE \u3oADVANCE \d3. Three omega scans consisting of 55, 54 and 55 data frames, respectively, were collected with a scan width of 2o and a detector-to-crystal distance, Dx, of 33mm. Each frame was exposed twice (for the purpose of de-zingering) for 180s. The data frames were processed and scaled using the DENZO software package. (Z. Otwinowski and W. Minor, Processing of X-Ray Diffraction Data Collected in Oscillation Mode, Methods in Enzymology, vol. 276: Macromolecular Crystallography, part A, 307-326, 1997, C.W. Carter, Jr. & R.M. Sweet, Eds., Academic Press). Data Reduction Of the 4748 reflections which were collected, 2708 were unique (RADVANCE \d1intADVANCE \u1 = 0.016). No decay correction was applied. The linear absorption coefficient, , for Mo-K radiation is 0.7 cmADVANCE \u3-1ADVANCE \d3 and no absorption correction was applied. The data were corrected for Lorentz and polarization effects. Structure Solution and Refinement The structure was solved by direct methodsADVANCE \u31ADVANCE \d3 and expanded using Fourier techniquesADVANCE \u32ADVANCE \d3. The non-hydrogen atoms were refined anisotropically. Some hydrogen atoms (OH group hydrogens) were refined isotropically, the rest were included in fixed positions. In the case of the methyl group hydrogen atoms, one hydrogen was located in the difference map and included at an idealized distance to set the orientation of the other two hydrogen atoms. The final cycle of full-matrix least-squares refinementADVANCE \u33ADVANCE \d3 was based on 2171 observed reflections (I > 3.00(I)) and 340 variable parameters and converged (largest parameter shift was 0.00 times its esd) with unweighted and weighted agreement factors of: R =  ||Fo| - |Fc|| /  |Fo| = 0.041 RADVANCE \d1wADVANCE \u1 = [(  w (|Fo| - |Fc|)ADVANCE \u32ADVANCE \d3 /  w FoADVANCE \u32ADVANCE \d3)]ADVANCE \u31/2ADVANCE \d3 = 0.043 The standard deviation of an observation of unit weightADVANCE \u34ADVANCE \d3 was 1.99. The weighting scheme was based on counting statistics and included a factor (p = 0.010) to downweight the intense reflections. Plots of  w (|Fo| - |Fc|)ADVANCE \u32ADVANCE \d3 versus |Fo|, reflection order in data collection, sin /, and various classes of indices showed no unusual trends. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.15 and -0.16 eADVANCE \u3-ADVANCE \d3/ADVANCE \u33ADVANCE \d3, respectively. Neutral atom scattering factors were taken from Cromer and WaberADVANCE \u35ADVANCE \d3. Anomalous dispersion effects were included in FcalcADVANCE \u36ADVANCE \d3; the values for f' and f" were those of Creagh and McAuleyADVANCE \u37ADVANCE \d3. The values for the mass attenuation coefficients are those of Creagh and HubbelADVANCE \u38ADVANCE \d3. All calculations were performed using the teXsanADVANCE \u39ADVANCE \d3 crystallographic software package of Molecular Structure Corporation. References (1) SIR92: Altomare, A., Burla, M.C., Camalli, M., Cascarano, M., Giacovazzo, C., Guagliardi, A., Polidori, G.; J. Appl. Cryst., 27, 435-436 (1994). (2) DIRDIF94: Beurskens, P.T., Admiraal, G., Beurskens, G., Bosman, W.P., de Gelder, R., Israel, R. and Smits, J.M.M.(1994). The DIRDIF-94 program system, Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands. (3) Least-Squares: Function minimized Sw(|FADVANCE \d1oADVANCE \u1|-|FADVANCE \d1cADVANCE \u1|)ADVANCE \u32ADVANCE \d3 where w = 4FADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3/sADVANCE \u32ADVANCE \d3(FADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3) and sADVANCE \u32ADVANCE \d3(FADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3) = [SADVANCE \u32ADVANCE \d3(C+RADVANCE \u32ADVANCE \d3B) + (pFADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3)ADVANCE \u32ADVANCE \d3]/LpADVANCE \u32ADVANCE \d3 S = Scan rate C = Total integrated peak count R = Ratio of scan time to background counting time B = Total background count Lp = Lorentz-polarization factor p = p-factor (4) Standard deviation of an observation of unit weight: [Sw(|FADVANCE \d1oADVANCE \u1|-|FADVANCE \d1cADVANCE \u1|)ADVANCE \u32ADVANCE \d3/(NADVANCE \d1oADVANCE \u1-NADVANCE \d1vADVANCE \u1)]ADVANCE \u31/2ADVANCE \d3 where NADVANCE \d1oADVANCE \u1 = number of observations and NADVANCE \d1vADVANCE \u1 = number of variables (5) Cromer, D. T. & Waber, J. T.; "International Tables for X-ray Crystallography", Vol. IV, The Kynoch Press, Birmingham, England, Table 2.2 A (1974). (6) Ibers, J. A. & Hamilton, W. C.; Acta Crystallogr., 17, 781 (1964). (7) Creagh, D. C. & McAuley, W.J .; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.6.8, pages 219-222 (1992). (8) Creagh, D. C. & Hubbell, J.H..; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.4.3, pages 200-206 (1992). (9) teXsan: Crystal Structure Analysis Package, Molecular Structure Corporation (1985 & 1992). EXPERIMENTAL DETAILS A. Crystal Data Empirical Formula CADVANCE \d332ADVANCE \u3HADVANCE \d352ADVANCE \u3OADVANCE \d34ADVANCE \u3 Formula Weight 500.76 Crystal Color, Habit colorless, plate Crystal Dimensions 0.05 X 0.12 X 0.19 mm Crystal System monoclinic Lattice Type Primitive Lattice Parameters a = 9.7381(2) b = 13.3319(4) c = 11.5709(3)  = 101.424(2)ADVANCE \u3oADVANCE \d3 V = 1472.46(6) ADVANCE \u33ADVANCE \d3 Space Group P2ADVANCE \d31ADVANCE \u3 (#4) Z value 2 DADVANCE \d1calcADVANCE \u1 1.129 g/cmADVANCE \u33ADVANCE \d3 FADVANCE \d1000ADVANCE \u1 552.00 (MoK) 0.72 cmADVANCE \u3-1ADVANCE \d3 B. Intensity Measurements Diffractometer Nonius KappaCCD Radiation MoK ( = 0.71069 ) graphite monochromated Take-off Angle 2.8ADVANCE \u3oADVANCE \d3 Crystal to Detector Distance 33 mm Temperature -90.0ADVANCE \u3oADVANCE \d3C Scan Type  Scan Rate 180s/frame Scan Width 2.0ADVANCE \u3oADVANCE \d3/frame 2ADVANCE \d1maxADVANCE \u1 50.0ADVANCE \u3oADVANCE \d3 No. of Reflections Measured Total: 4748 Corrections Lorentz-polarization C. Structure Solution and Refinement Structure Solution Direct Methods (SIR92) Refinement Full-matrix least-squares Function Minimized  w (|Fo| - |Fc|)ADVANCE \u32ADVANCE \d3 Least Squares Weights 1/ADVANCE \u32ADVANCE \d3(Fo) p-factor 0.0100 Anomalous Dispersion All non-hydrogen atoms No. Observations (I>3.00(I)) 2171 No. Variables 340 Reflection/Parameter Ratio 6.39 Residuals: R; Rw 0.041; 0.043 Goodness of Fit Indicator 1.99 Max Shift/Error in Final Cycle 0.00 Maximum peak in Final Diff. Map 0.15 eADVANCE \u3-ADVANCE \d3/ADVANCE \u33ADVANCE \d3 Minimum peak in Final Diff. Map -0.16 eADVANCE \u3-ADVANCE \d3/ADVANCE \u33ADVANCE \d3 Table 1. Atomic coordinates and BADVANCE \d1isoADVANCE \u1/BADVANCE \d1eqADVANCE \u1 atom x y z BADVANCE \d1eqADVANCE \u1 ------------------------------------------------------------------------------------------ O(1) 0.8727(2) 0.7035 -0.0938(2) 3.03(5) O(2) 0.6094(2) 0.7626(3) -0.0948(2) 3.52(5) O(3) 0.6482(2) 0.2768(2) 0.2293(2) 3.37(5) O(4) 0.9070(2) 0.2409(3) 0.1965(2) 3.83(5) C(1) 0.8100(3) 0.6123(3) -0.0612(2) 2.58(6) C(2) 0.9193(3) 0.5272(3) -0.0414(3) 3.22(7) C(3) 0.8480(4) 0.4334(4) -0.1027(4) 5.9(1) C(4) 0.7099(5) 0.4051(4) -0.0701(5) 6.8(1) C(5) 0.6423(4) 0.4468(4) 0.0031(5) 6.4(1) C(6) 0.6866(3) 0.5307(4) 0.0869(3) 4.61(9) C(7) 0.7279(2) 0.6329(3) 0.0370(2) 2.74(7) C(8) 0.5871(3) 0.6803(3) -0.0209(3) 3.43(7) C(9) 0.8098(3) 0.6980(3) 0.1400(3) 3.55(7) C(10) 0.7822(4) 0.8108(4) 0.1310(3) 5.01(9) C(11) 0.9694(3) 0.6817(3) 0.1636(3) 3.31(7) C(12) 1.0170(3) 0.5754(3) 0.1845(2) 3.11(7) C(13) 0.9925(3) 0.5014(3) 0.0839(3) 3.20(7) C(14) 1.1409(3) 0.5336(3) 0.1406(3) 3.03(7) C(15) 1.2247(3) 0.5985(3) 0.0729(3) 4.04(8) C(16) 1.2305(3) 0.4584(3) 0.2187(3) 4.48(8) C(17) 0.7344(3) 0.3145(3) 0.3356(2) 2.57(6) C(18) 0.6395(3) 0.3603(3) 0.4150(3) 3.09(7) C(19) 0.7038(4) 0.4617(4) 0.4584(4) 5.5(1) C(20) 0.8556(5) 0.4573(4) 0.5173(4) 6.5(1) C(21) 0.9425(4) 0.3811(5) 0.5379(3) 5.9(1) C(22) 0.9152(3) 0.2713(4) 0.5162(3) 4.25(8) C(23) 0.8434(2) 0.2372(3) 0.3905(2) 2.67(6) C(24) 0.9619(2) 0.2403(3) 0.3199(2) 3.42(7) C(25) 0.7846(3) 0.1290(3) 0.3974(3) 3.24(7) C(26) 0.7867(3) 0.0608(3) 0.2915(3) 4.59(9) C(27) 0.6343(3) 0.1264(3) 0.4215(3) 3.41(8) C(28) 0.6094(3) 0.1871(3) 0.5249(3) 3.30(7) C(29) 0.6125(3) 0.3003(3) 0.5192(3) 3.29(7) C(30) 0.4765(3) 0.2459(3) 0.5234(3) 3.58(7) C(31) 0.3605(3) 0.2440(4) 0.4178(3) 4.83(9) C(32) 0.4241(4) 0.2516(4) 0.6385(3) 5.7(1) H(1) 0.7421 0.5933 -0.1284 3.0971 H(2) 0.9906 0.5456 -0.0827 3.8645 H(3) 0.8315 0.4446 -0.1853 7.1147 H(4) 0.9105 0.3785 -0.0832 7.1147 H(5) 0.6658 0.3477 -0.1097 8.1492 H(6) 0.5519 0.4200 0.0032 7.6580 H(7) 0.6112 0.5438 0.1258 5.5324 H(8) 0.7655 0.5081 0.1427 5.5324 H(9) 0.5408 0.7040 0.0388 4.1220 H(10) 0.5305 0.6312 -0.0672 4.1220 H(11) 0.7797 0.6763 0.2092 4.2635 H(12) 0.6880 0.8238 0.1370 6.0125 H(13) 0.8438 0.8442 0.1931 6.0125 H(14) 0.7978 0.8346 0.0573 6.0125 H(15) 1.0031 0.7059 0.0972 3.9746 H(16) 1.0096 0.7197 0.2313 3.9746 H(17) 1.0046 0.5484 0.2577 3.7370 H(18) 0.9699 0.4362 0.1074 3.8398 H(19) 1.2601 0.5584 0.0176 4.8438 H(20) 1.3005 0.6282 0.1262 4.8438 H(21) 1.1662 0.6496 0.0325 4.8438 H(22) 1.2964 0.4928 0.2768 5.3774 H(23) 1.1728 0.4172 0.2562 5.3774 H(24) 1.2789 0.4178 0.1723 5.3774 H(25) 0.533(3) 0.775(3) -0.141(3) 5.1(9) H(26) 0.806(3) 0.743(3) -0.119(3) 4.7(9) H(27) 0.7855 0.3690 0.3123 3.0803 H(28) 0.5511 0.3736 0.3659 3.7028 H(29) 0.6950 0.5054 0.3925 6.6400 H(30) 0.6525 0.4882 0.5133 6.6400 H(31) 0.8955 0.5202 0.5441 7.8454 H(32) 1.0366 0.3980 0.5716 7.1244 H(33) 1.0031 0.2381 0.5350 5.1058 H(34) 0.8575 0.2498 0.5687 5.1058 H(35) 1.0198 0.1829 0.3391 4.1072 H(36) 1.0160 0.2993 0.3405 4.1072 H(37) 0.8427 0.0977 0.4632 3.8892 H(38) 0.7280 0.0883 0.2235 5.5052 H(39) 0.7535 -0.0039 0.3067 5.5052 H(40) 0.8798 0.0556 0.2786 5.5052 H(41) 0.5728 0.1507 0.3531 4.0865 H(42) 0.6120 0.0585 0.4348 4.0865 H(43) 0.6504 0.1599 0.5996 3.9596 H(44) 0.6535 0.3299 0.5926 3.9475 H(45) 0.3983 0.2493 0.3484 5.7996 H(46) 0.2990 0.2987 0.4214 5.7996 H(47) 0.3102 0.1828 0.4164 5.7996 H(48) 0.3674 0.1947 0.6452 6.8856 H(49) 0.5018 0.2526 0.7028 6.8856 H(50) 0.3704 0.3109 0.6395 6.8856 H(51) 0.705(3) 0.256(3) 0.186(3) 5.2(9) H(52) 0.981(3) 0.231(3) 0.161(3) 4.1(7) X-RAY CRYSTALLOGRAPHY REPORT FOR ACETAL 17  EMBED ChemDraw.Document.4.5  Data Collection A colorless plate crystal of CADVANCE \d315ADVANCE \u3HADVANCE \d324ADVANCE \u3OADVANCE \d34ADVANCE \u3 having approximate dimensions of 0.05 x 0.20 x 0.24 mm was mounted on a glass fiber. All measurements were made on a Nonius KappaCCD diffractometer with graphite monochromated Mo-K radiation. Cell constants and an orientation matrix for data collection, obtained from a least-squares refinement using ten (1o in , 10s exposure, de-zingered) data frames, corresponded to a primitive orthorhombic cell with dimensions: a = 5.8792(2) , b = 7.0770(3) , c = 34.695(1) , and V = 1443.56(8) ADVANCE \u33ADVANCE \d3. For Z = 4 and F.W. = 268.35, the calculated density is 1.24 g/cmADVANCE \u33ADVANCE \d3. The systematic absences of: h00: h = 2n+1, 0k0: k = 2n+1, 00l: l = 2n+1; uniquely determine the space group to be: P2ADVANCE \d31ADVANCE \u32ADVANCE \d31ADVANCE \u32ADVANCE \d31ADVANCE \u3 (#19). The data were collected at a temperature of -90 + 1ADVANCE \u3oADVANCE \d3C to a maximum 2 value of 55.0ADVANCE \u3oADVANCE \d3. Three omega scans consisting of 133, 172 and 172 data frames, respectively, were collected with a scan width of 0.8o and a detector-to-crystal distance, Dx, of 45mm. Each frame was exposed twice (for the purpose of de-zingering) for 48s. The data frames were processed and scaled using the DENZO software package. (Z. Otwinowski and W. Minor, Processing of X-Ray Diffraction Data Collected in Oscillation Mode, Methods in Enzymology, vol. 276: Macromolecular Crystallography, part A, 307-326, 1997, C.W. Carter, Jr. & R.M. Sweet, Eds., Academic Press). Data Reduction Of the 3333 reflections which were collected, 1994 were unique (RADVANCE \d1intADVANCE \u1 = 0.046). No decay correction was applied. The linear absorption coefficient, , for Mo-K radiation is 0.9 cmADVANCE \u3-1ADVANCE \d3 and no absorption correction was applied. The data were corrected for Lorentz and polarization effects. Structure Solution and Refinement The structure was solved by direct methodsADVANCE \u31ADVANCE \d3 and expanded using Fourier techniquesADVANCE \u32ADVANCE \d3. The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included but not refined. In the case of the methyl group hydrogen atoms, one hydrogen was located in the difference map and included at an idealized distance to set the orientation of the other two hydrogen atoms. The final cycle of full-matrix least-squares refinementADVANCE \u33ADVANCE \d3 was based on 1188 observed reflections (I > 3.00(I)) and 172 variable parameters and converged (largest parameter shift was 0.00 times its esd) with unweighted and weighted agreement factors of: R =  ||Fo| - |Fc|| /  |Fo| = 0.052 RADVANCE \d1wADVANCE \u1 = [(  w (|Fo| - |Fc|)ADVANCE \u32ADVANCE \d3 /  w FoADVANCE \u32ADVANCE \d3)]ADVANCE \u31/2ADVANCE \d3 = 0.055 The standard deviation of an observation of unit weightADVANCE \u34ADVANCE \d3 was 2.38. The weighting scheme was based on counting statistics and included a factor (p = 0.010) to downweight the intense reflections. Plots of  w (|Fo| - |Fc|)ADVANCE \u32ADVANCE \d3 versus |Fo|, reflection order in data collection, sin /, and various classes of indices showed no unusual trends. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.24 and -0.25 eADVANCE \u3-ADVANCE \d3/ADVANCE \u33ADVANCE \d3, respectively. Neutral atom scattering factors were taken from Cromer and WaberADVANCE \u35ADVANCE \d3. Anomalous dispersion effects were included in FcalcADVANCE \u36ADVANCE \d3; the values for f' and f" were those of Creagh and McAuleyADVANCE \u37ADVANCE \d3. The values for the mass attenuation coefficients are those of Creagh and HubbelADVANCE \u38ADVANCE \d3. All calculations were performed using the teXsanADVANCE \u39ADVANCE \d3 crystallographic software package of Molecular Structure Corporation. References (1) SIR92: Altomare, A., Burla, M.C., Camalli, M., Cascarano, M., Giacovazzo, C., Guagliardi, A., Polidori, G.; J. Appl. Cryst., 27, 435-436 (1994). (2) DIRDIF94: Beurskens, P.T., Admiraal, G., Beurskens, G., Bosman, W.P., de Gelder, R., Israel, R. and Smits, J.M.M.(1994). The DIRDIF-94 program system, Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands. (3) Least-Squares: Function minimized Sw(|FADVANCE \d1oADVANCE \u1|-|FADVANCE \d1cADVANCE \u1|)ADVANCE \u32ADVANCE \d3 where w = 4FADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3/sADVANCE \u32ADVANCE \d3(FADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3) and sADVANCE \u32ADVANCE \d3(FADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3) = [SADVANCE \u32ADVANCE \d3(C+RADVANCE \u32ADVANCE \d3B) + (pFADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3)ADVANCE \u32ADVANCE \d3]/LpADVANCE \u32ADVANCE \d3 S = Scan rate C = Total integrated peak count R = Ratio of scan time to background counting time B = Total background count Lp = Lorentz-polarization factor p = p-factor (4) Standard deviation of an observation of unit weight: [Sw(|FADVANCE \d1oADVANCE \u1|-|FADVANCE \d1cADVANCE \u1|)ADVANCE \u32ADVANCE \d3/(NADVANCE \d1oADVANCE \u1-NADVANCE \d1vADVANCE \u1)]ADVANCE \u31/2ADVANCE \d3 where NADVANCE \d1oADVANCE \u1 = number of observations and NADVANCE \d1vADVANCE \u1 = number of variables (5) Cromer, D. T. & Waber, J. T.; "International Tables for X-ray Crystallography", Vol. IV, The Kynoch Press, Birmingham, England, Table 2.2 A (1974). (6) Ibers, J. A. & Hamilton, W. C.; Acta Crystallogr., 17, 781 (1964). (7) Creagh, D. C. & McAuley, W.J .; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.6.8, pages 219-222 (1992). (8) Creagh, D. C. & Hubbell, J.H..; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.4.3, pages 200-206 (1992). (9) teXsan: Crystal Structure Analysis Package, Molecular Structure Corporation (1985 & 1992). EXPERIMENTAL DETAILS A. Crystal Data Empirical Formula CADVANCE \d315ADVANCE \u3HADVANCE \d324ADVANCE \u3OADVANCE \d34ADVANCE \u3 Formula Weight 268.35 Crystal Color, Habit colorless, plates Crystal Dimensions 0.05 X 0.20 X 0.24 mm Crystal System orthorhombic Lattice Type Primitive Lattice Parameters a = 5.8792(2) b = 7.0770(3) c = 34.695(1) V = 1443.56(8) ADVANCE \u33ADVANCE \d3 Space Group P2ADVANCE \d31ADVANCE \u32ADVANCE \d31ADVANCE \u32ADVANCE \d31ADVANCE \u3 (#19) Z value 4 DADVANCE \d1calcADVANCE \u1 1.235 g/cmADVANCE \u33ADVANCE \d3 FADVANCE \d1000ADVANCE \u1 584.00 (MoK) 0.88 cmADVANCE \u3-1ADVANCE \d3 B. Intensity Measurements Diffractometer Nonius KappaCCD Radiation MoK ( = 0.71069 ) graphite monochromated Take-off Angle 2.8ADVANCE \u3oADVANCE \d3 Crystal to Detector Distance 45 mm Temperature -90.0ADVANCE \u3oADVANCE \d3C Scan Rate 48s/frame Scan Width 0.8ADVANCE \u3oADVANCE \d3/frame 2ADVANCE \d1maxADVANCE \u1 55.0ADVANCE \u3oADVANCE \d3 No. of Reflections Measured Total: 3333 Corrections Lorentz-polarization C. Structure Solution and Refinement Structure Solution Direct Methods (SIR92) Refinement Full-matrix least-squares Function Minimized  w (|Fo| - |Fc|)ADVANCE \u32ADVANCE \d3 Least Squares Weights 1/ ADVANCE \u32ADVANCE \d3(Fo) p-factor 0.0100 Anomalous Dispersion All non-hydrogen atoms No. Observations (I>3.00(I)) 1188 No. Variables 172 Reflection/Parameter Ratio 6.91 Residuals: R; Rw 0.052; 0.055 Goodness of Fit Indicator 2.38 Max Shift/Error in Final Cycle 0.00 Maximum peak in Final Diff. Map 0.24 eADVANCE \u3-ADVANCE \d3/ADVANCE \u33ADVANCE \d3 Minimum peak in Final Diff. Map -0.25 eADVANCE \u3-ADVANCE \d3/ADVANCE \u33ADVANCE \d3 Table 1. Atomic coordinates and BADVANCE \d1isoADVANCE \u1/BADVANCE \d1eqADVANCE \u1 atom x y z BADVANCE \d1eqADVANCE \u1 ------------------------------------------------------------------------------------------ O(1) -0.2389(4) 0.3153(4) 0.30847(6) 2.64(6) O(2) 0.0588(4) 0.2579(4) 0.34940(6) 2.73(6) O(3) -0.1105(5) -0.1129(5) 0.30737(8) 4.06(8) O(4) -0.4884(5) -0.1143(4) 0.31139(7) 3.53(7) C(1) -0.1803(7) 0.2690(6) 0.34778(10) 2.39(10) C(2) -0.2662(7) 0.4256(5) 0.37406(9) 2.61(10) C(3) -0.1656(7) 0.4216(6) 0.41410(10) 2.27(9) C(4) -0.1968(6) 0.2540(6) 0.44089(10) 2.50(9) C(5) -0.3312(8) 0.0812(6) 0.4293(1) 3.2(1) C(6) -0.2409(8) -0.0256(6) 0.3944(1) 3.0(1) C(7) -0.3001(7) 0.0763(6) 0.35590(10) 2.59(9) C(8) -0.0354(8) 0.3767(7) 0.2904(1) 3.7(1) C(9) 0.1476(8) 0.309(1) 0.3136(1) 7.1(2) C(10) -0.3009(7) 0.4429(6) 0.45099(10) 2.59(10) C(11) -0.1923(7) 0.5503(6) 0.4835(1) 3.28(10) C(12) -0.5556(7) 0.4692(7) 0.4494(1) 3.9(1) C(13) 0.0099(8) -0.0777(6) 0.3987(1) 3.3(1) C(14) -0.2833(8) -0.0548(7) 0.3226(1) 2.9(1) C(15) -0.4967(7) -0.2452(6) 0.2802(1) 4.0(1) H(1) -0.2298 0.5437 0.3626 3.1314 H(2) -0.4267 0.4140 0.3762 3.1314 H(3) -0.0181 0.4761 0.4155 2.7192 H(4) -0.0648 0.2253 0.4555 2.9956 H(5) -0.3326 -0.0033 0.4506 3.8970 H(6) -0.4822 0.1203 0.4237 3.8970 H(7) -0.3213 -0.1420 0.3938 3.5754 H(8) -0.4572 0.1060 0.3579 3.1086 H(9) -0.0250 0.3255 0.2651 4.4920 H(10) -0.0319 0.5107 0.2890 4.4920 H(11) 0.2579 0.4061 0.3168 8.5283 H(12) 0.2162 0.2027 0.3017 8.5283 H(13) -0.0315 0.5442 0.4810 3.9361 H(14) -0.2368 0.4961 0.5073 3.9361 H(15) -0.2399 0.6785 0.4826 3.9361 H(16) -0.6228 0.4163 0.4718 4.6729 H(17) -0.5900 0.6002 0.4481 4.6729 H(18) -0.6142 0.4077 0.4271 4.6729 H(19) 0.0575 -0.1488 0.3769 3.9954 H(20) 0.0300 -0.1510 0.4214 3.9954 H(21) 0.0983 0.0344 0.4005 3.9954 H(22) -0.4978 -0.1782 0.2565 4.8259 H(23) -0.6308 -0.3195 0.2822 4.8259 H(24) -0.3671 -0.3253 0.2812 4.8259 X-RAY CRYSTALLOGRAPHY REPORT FOR 21  EMBED ChemDraw.Document.4.5  Data Collection A colorless plate crystal of CADVANCE \d318ADVANCE \u3HADVANCE \d326ADVANCE \u3OADVANCE \d34ADVANCE \u3 having approximate dimensions of 0.07 x 0.17 x 0.19 mm was mounted on a glass fiber. All measurements were made on a Nonius KappaCCD diffractometer with graphite monochromated Mo-K radiation. Cell constants and an orientation matrix for data collection, obtained from a least-squares refinement using ten (1o in , 10s exposure, de-zingered) data frames, corresponded to a primitive orthorhombic cell with dimensions: a = 6.0539(2) , b = 12.3425(3) , c = 23.046(1) , and V = 1722.03(9) ADVANCE \u33ADVANCE \d3. For Z = 4 and F.W. = 306.40, the calculated density is 1.18 g/cmADVANCE \u33ADVANCE \d3. The systematic absences of: h00: h = 2n+1, 0k0: k = 2n+1, 00l: l = 2n+1; uniquely determine the space group to be: P2ADVANCE \d31ADVANCE \u32ADVANCE \d31ADVANCE \u32ADVANCE \d31ADVANCE \u3 (#19). In this acentric space group, both enantiomers refine identically. The data were collected at a temperature of -90 + 1ADVANCE \u3oADVANCE \d3C to a maximum 2 value of 50.1ADVANCE \u3oADVANCE \d3. Three omega scans consisting of 82, 77, and 77 data frames, respectively, were collected with a scan width of 1.4o and a detector-to-crystal distance, Dx, of 35mm. Each frame was exposed twice (for the purpose of de-zingering) for 84s. The data frames were processed and scaled using the DENZO software package. (Z. Otwinowski and W. Minor, Processing of X-Ray Diffraction Data Collected in Oscillation Mode, Methods in Enzymology, vol. 276: Macromolecular Crystallography, part A, 307-326, 1997, C.W. Carter, Jr. & R.M. Sweet, Eds., Academic Press). Data Reduction Of the 3072 reflections which were collected, 1814 were unique (RADVANCE \d1intADVANCE \u1 = 0.025). No decay correction was applied. The linear absorption coefficient, , for Mo-K radiation is 0.8 cmADVANCE \u3-1ADVANCE \d3 and no absorption correction was applied. The data were corrected for Lorentz and polarization effects. Structure Solution and Refinement The structure was solved by direct methodsADVANCE \u31ADVANCE \d3 and expanded using Fourier techniquesADVANCE \u32ADVANCE \d3. The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were refined isotropically. The final cycle of full-matrix least-squares refinementADVANCE \u33ADVANCE \d3 was based on 1422 observed reflections (I > 3.00(I)) and 303 variable parameters and converged (largest parameter shift was 0.00 times its esd) with unweighted and weighted agreement factors of: R =  ||Fo| - |Fc|| /  |Fo| = 0.036 RADVANCE \d1wADVANCE \u1 = [(  w (|Fo| - |Fc|)ADVANCE \u32ADVANCE \d3 /  w FoADVANCE \u32ADVANCE \d3)]ADVANCE \u31/2ADVANCE \d3 = 0.036 The standard deviation of an observation of unit weightADVANCE \u34ADVANCE \d3 was 1.88. The weighting scheme was based on counting statistics and included a factor (p = 0.020) to downweight the intense reflections. Plots of  w (|Fo| - |Fc|)ADVANCE \u32ADVANCE \d3 versus |Fo|, reflection order in data collection, sin / and various classes of indices showed no unusual trends. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.19 and -0.19 eADVANCE \u3-ADVANCE \d3/ADVANCE \u33ADVANCE \d3, respectively. Neutral atom scattering factors were taken from Cromer and WaberADVANCE \u35ADVANCE \d3. Anomalous dispersion effects were included in FcalcADVANCE \u36ADVANCE \d3; the values for f' and f" were those of Creagh and McAuleyADVANCE \u37ADVANCE \d3. The values for the mass attenuation coefficients are those of Creagh and HubbelADVANCE \u38ADVANCE \d3. All calculations were performed using the teXsanADVANCE \u39ADVANCE \d3 crystallographic software package of Molecular Structure Corporation. References (1) SIR92: Altomare, A., Burla, M.C., Camalli, M., Cascarano, M., Giacovazzo, C., Guagliardi, A., Polidori, G.; J. Appl. Cryst., 27, 435-436 (1994). (2) DIRDIF94: Beurskens, P.T., Admiraal, G., Beurskens, G., Bosman, W.P., de Gelder, R., Israel, R. and Smits, J.M.M.(1994). The DIRDIF-94 program system, Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands. (3) Least-Squares: Function minimized Sw(|FADVANCE \d1oADVANCE \u1|-|FADVANCE \d1cADVANCE \u1|)ADVANCE \u32ADVANCE \d3 where w = 4FADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3/sADVANCE \u32ADVANCE \d3(FADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3) and sADVANCE \u32ADVANCE \d3(FADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3) = [SADVANCE \u32ADVANCE \d3(C+RADVANCE \u32ADVANCE \d3B) + (pFADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3)ADVANCE \u32ADVANCE \d3]/LpADVANCE \u32ADVANCE \d3 S = Scan rate C = Total integrated peak count R = Ratio of scan time to background counting time B = Total background count Lp = Lorentz-polarization factor p = p-factor (4) Standard deviation of an observation of unit weight: [Sw(|FADVANCE \d1oADVANCE \u1|-|FADVANCE \d1cADVANCE \u1|)ADVANCE \u32ADVANCE \d3/(NADVANCE \d1oADVANCE \u1-NADVANCE \d1vADVANCE \u1)]ADVANCE \u31/2ADVANCE \d3 where NADVANCE \d1oADVANCE \u1 = number of observations and NADVANCE \d1vADVANCE \u1 = number of variables (5) Cromer, D. T. & Waber, J. T.; "International Tables for X-ray Crystallography", Vol. IV, The Kynoch Press, Birmingham, England, Table 2.2 A (1974). (6) Ibers, J. A. & Hamilton, W. C.; Acta Crystallogr., 17, 781 (1964). (7) Creagh, D. C. & McAuley, W.J .; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.6.8, pages 219-222 (1992). (8) Creagh, D. C. & Hubbell, J.H..; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.4.3, pages 200-206 (1992). (9) teXsan: Crystal Structure Analysis Package, Molecular Structure Corporation (1985 & 1992). EXPERIMENTAL DETAILS A. Crystal Data Empirical Formula CADVANCE \d318ADVANCE \u3HADVANCE \d326ADVANCE \u3OADVANCE \d34ADVANCE \u3 Formula Weight 306.40 Crystal Color, Habit colorless, plate Crystal Dimensions 0.07 X 0.17 X 0.19 mm Crystal System orthorhombic Lattice Type Primitive Lattice Parameters a = 6.0539(2) b = 12.3425(3) c = 23.046(1) V = 1722.03(9) ADVANCE \u33ADVANCE \d3 Space Group P2ADVANCE \d31ADVANCE \u32ADVANCE \d31ADVANCE \u32ADVANCE \d31ADVANCE \u3 (#19) Z value 4 DADVANCE \d1calcADVANCE \u1 1.182 g/cmADVANCE \u33ADVANCE \d3 FADVANCE \d1000ADVANCE \u1 664.00 (MoK) 0.82 cmADVANCE \u3-1ADVANCE \d3 B. Intensity Measurements Diffractometer Nonius KappaCCD Radiation MoK ( = 0.71069 ) graphite monochromated Take-off Angle 2.8ADVANCE \u3oADVANCE \d3 Crystal to Detector Distance 35 mm Temperature -90.0ADVANCE \u3oADVANCE \d3C Scan Rate 84s/frame Scan Width 1.4ADVANCE \u3oADVANCE \d3/frame 2ADVANCE \d1maxADVANCE \u1 50.1ADVANCE \u3oADVANCE \d3 No. of Reflections Measured Total: 3072 Corrections Lorentz-polarization C. Structure Solution and Refinement Structure Solution Direct Methods (SIR92) Refinement Full-matrix least-squares Function Minimized  w (|Fo| - |Fc|)ADVANCE \u32ADVANCE \d3 Least Squares Weights 1/ ADVANCE \u32ADVANCE \d3(Fo) p-factor 0.0200 Anomalous Dispersion All non-hydrogen atoms No. Observations (I>3.00(I)) 1422 No. Variables 303 Reflection/Parameter Ratio 4.69 Residuals: R; Rw 0.036; 0.036 Goodness of Fit Indicator 1.88 Max Shift/Error in Final Cycle 0.00 Maximum peak in Final Diff. Map 0.19 eADVANCE \u3-ADVANCE \d3/ADVANCE \u33ADVANCE \d3 Minimum peak in Final Diff. Map -0.19 eADVANCE \u3-ADVANCE \d3/ADVANCE \u33ADVANCE \d3 Table 1. Atomic coordinates and BADVANCE \d1isoADVANCE \u1/BADVANCE \d1eqADVANCE \u1 atom x y z BADVANCE \d1eqADVANCE \u1 ----------------------------------------------------------------------------------------- O(1) -0.0465(3) -0.0325(1) 0.29639(7) 3.31(4) O(2) 0.3870(3) 0.0385(1) 0.22267(8) 3.83(4) O(3) 0.3276(4) -0.2450(2) 0.08171(8) 6.48(7) O(4) -0.0163(3) -0.2703(2) 0.11030(7) 3.93(5) C(1) 0.2376(4) -0.1603(2) 0.2739(1) 2.25(5) C(2) 0.2414(4) -0.2585(2) 0.3175(1) 2.57(5) C(3) 0.3728(5) -0.2385(2) 0.3737(1) 2.94(6) C(4) 0.2532(5) -0.1720(2) 0.4192(1) 2.92(6) C(5) 0.2106(5) -0.0531(2) 0.4080(1) 2.81(6) C(6) 0.2814(5) -0.0058(2) 0.3506(1) 2.60(6) C(7) 0.1454(4) -0.0608(2) 0.3045(1) 2.46(6) C(8) 0.0112(6) -0.3022(3) 0.3309(1) 3.81(7) C(9) 0.3642(5) -0.0858(2) 0.4563(1) 3.48(6) C(10) 0.2734(7) -0.0731(3) 0.5174(1) 4.60(9) C(11) 0.6091(5) -0.0652(3) 0.4520(2) 4.41(9) C(12) 0.4717(4) -0.1461(2) 0.2477(1) 2.33(5) C(13) 0.4873(5) -0.2330(2) 0.1993(1) 2.75(6) C(14) 0.2479(4) -0.2638(2) 0.18382(10) 2.40(5) C(15) 0.1024(5) -0.1865(2) 0.2193(1) 2.66(6) C(16) 0.5131(5) -0.0367(2) 0.2214(1) 3.02(6) C(17) 0.1980(5) -0.2583(2) 0.1200(1) 2.92(6) C(18) -0.0904(7) -0.2672(4) 0.0506(1) 4.48(9) H(1) 0.317(4) -0.312(2) 0.296(1) 3.0(6) H(2) 0.404(5) -0.314(2) 0.389(1) 4.4(6) H(3) 0.522(5) -0.209(2) 0.3644(10) 2.6(5) H(4) 0.136(5) -0.208(2) 0.438(1) 3.4(6) H(5) 0.071(4) -0.026(2) 0.4189(9) 1.3(4) H(6) 0.254(5) 0.076(2) 0.349(1) 3.9(5) H(7) 0.436(4) -0.016(2) 0.3452(9) 1.9(5) H(8) -0.081(4) -0.246(2) 0.349(1) 3.1(6) H(9) -0.057(5) -0.338(2) 0.295(1) 4.2(6) H(10) 0.026(5) -0.363(2) 0.360(1) 3.9(6) H(11) 0.301(5) 0.002(2) 0.532(1) 4.6(7) H(12) 0.102(7) -0.088(2) 0.517(1) 5.7(8) H(13) 0.340(5) -0.126(2) 0.543(1) 5.2(7) H(14) 0.675(5) -0.079(2) 0.412(1) 4.7(7) H(15) 0.681(7) -0.116(3) 0.479(2) 7.0(10) H(16) 0.646(5) 0.005(2) 0.466(1) 5.0(7) H(17) 0.589(4) -0.152(2) 0.2750(10) 1.9(5) H(18) 0.560(5) -0.211(2) 0.164(1) 3.8(6) H(19) 0.571(4) -0.297(2) 0.211(1) 3.4(6) H(20) 0.222(4) -0.341(2) 0.1955(9) 2.7(5) H(21) -0.041(5) -0.219(2) 0.227(1) 2.8(5) H(22) 0.088(4) -0.117(2) 0.195(1) 3.2(5) H(23) 0.657(5) -0.031(2) 0.201(1) 3.6(6) H(24) -0.048(6) -0.200(3) 0.036(1) 5.4(8) H(25) -0.016(7) -0.326(3) 0.028(2) 7.2(9) H(26) -0.249(6) -0.265(2) 0.052(1) 5.4(8) X-RAY CRYSTALLOGRAPHY REPORT FOR DIESRER 27  EMBED ChemDraw.Document.4.5  Data Collection A colorless needle crystal of CADVANCE \d335ADVANCE \u3HADVANCE \d338ADVANCE \u3OADVANCE \d37ADVANCE \u3BrADVANCE \d32ADVANCE \u3 having approximate dimensions of 0.05 x 0.05 x 0.16 mm was mounted on a glass fiber. All measurements were made on a Nonius KappaCCD diffractometer with graphite monochromated Mo-K radiation. Cell constants and an orientation matrix for data collection, obtained from a least-squares refinement using ten (1o in , 10s exposure, de-zingered) data frames, corresponded to a primitive orthorhombic cell with dimensions: a = 7.0834(3) , b = 12.7467(4) , c = 36.377(1) , and V = 3284.4(2) ADVANCE \u33ADVANCE \d3. For Z = 4 and F.W. = 730.49, the calculated density is 1.48 g/cmADVANCE \u33ADVANCE \d3. The systematic absences of: h00: h = 2n+1, 0k0: k = 2n+1, 00l: l = 2n+1; uniquely determine the space group to be: P2ADVANCE \d31ADVANCE \u32ADVANCE \d31ADVANCE \u32ADVANCE \d31ADVANCE \u3 (#19). The data were collected at a temperature of -90 + 1ADVANCE \u3oADVANCE \d3C to a maximum 2 value of 50.1ADVANCE \u3oADVANCE \d3. Two omega scans consisting of 163 and 163 data frames, respectively, were collected with a scan width of 0.9o and a detector-to-crystal distance, Dx, of 50mm. Each frame was exposed twice (for the purpose of de-zingering) for 81s. The data frames were processed and scaled using the DENZO software package. (Z. Otwinowski and W. Minor, Processing of X-Ray Diffraction Data Collected in Oscillation Mode, Methods in Enzymology, vol. 276: Macromolecular Crystallography, part A, 307-326, 1997, C.W. Carter, Jr. & R.M. Sweet, Eds., Academic Press). Data Reduction Of the 5842 reflections which were collected, 3378 were unique (RADVANCE \d1intADVANCE \u1 = 0.112). No decay correction was applied. The linear absorption coefficient, , for Mo-K radiation is 25.2 cmADVANCE \u3-1ADVANCE \d3 and a SORTAV absorption correction was applied [SORTAV: Blessing, R.H.; Acta Cryst., A51, 33-37 (1995). Blessing, R.H.; J. Appl. Cryst., 30, 421-426 (1997)]. The data were corrected for Lorentz and polarization effects. A correction for secondary extinction was applied (coefficient = 6.99826e-08). Structure Solution and Refinement The structure was solved by direct methodsADVANCE \u31ADVANCE \d3 and expanded using Fourier techniquesADVANCE \u32ADVANCE \d3. The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included but not refined. In the case of the methyl group hydrogen atoms, one hydrogen was located in the difference map and included at an idealized distance to set the orientation of the other two hydrogen atoms. The final cycle of full-matrix least-squares refinementADVANCE \u33ADVANCE \d3 was based on 1514 observed reflections (I > 3.00(I)) and 397 variable parameters and converged (largest parameter shift was 0.00 times its esd) with unweighted and weighted agreement factors of: R =  ||Fo| - |Fc|| /  |Fo| = 0.040 RADVANCE \d1wADVANCE \u1 = [(  w (|Fo| - |Fc|)ADVANCE \u32ADVANCE \d3 /  w FoADVANCE \u32ADVANCE \d3)]ADVANCE \u31/2ADVANCE \d3 = 0.034 The standard deviation of an observation of unit weightADVANCE \u34ADVANCE \d3 was 1.34. Refinement of the Flack parameter supports the assigned stereochemistry. In addition the other enantiomer yielded R/Rw values equal to 5.7 and 5.3 per cent, respectively, upon least squares refinement. The weighting scheme was based on counting statistics and included a factor (p = 0.020) to downweight the intense reflections. Plots of  w (|Fo| - |Fc|)ADVANCE \u32ADVANCE \d3 versus |Fo|, reflection order in data collection, sin / and various classes of indices showed no unusual trends. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.34 and -0.38 eADVANCE \u3-ADVANCE \d3/ADVANCE \u33ADVANCE \d3, respectively. Neutral atom scattering factors were taken from Cromer and WaberADVANCE \u35ADVANCE \d3. Anomalous dispersion effects were included in FcalcADVANCE \u36ADVANCE \d3; the values for f' and f" were those of Creagh and McAuleyADVANCE \u37ADVANCE \d3. The values for the mass attenuation coefficients are those of Creagh and HubbelADVANCE \u38ADVANCE \d3. All calculations were performed using the teXsanADVANCE \u39ADVANCE \d3 crystallographic software package of Molecular Structure Corporation. References (1) SIR92: Altomare, A., Burla, M.C., Camalli, M., Cascarano, M., Giacovazzo, C., Guagliardi, A., Polidori, G. (1994). J. Appl. Cryst., in preparation. (2) DIRDIF94: Beurskens, P.T., Admiraal, G., Beurskens, G., Bosman, W.P., de Gelder, R., Israel, R. and Smits, J.M.M.(1994). The DIRDIF-94 program system, Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands. (3) Least-Squares: Function minimized Sw(|FADVANCE \d1oADVANCE \u1|-|FADVANCE \d1cADVANCE \u1|)ADVANCE \u32ADVANCE \d3 where w = 4FADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3/sADVANCE \u32ADVANCE \d3(FADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3) and sADVANCE \u32ADVANCE \d3(FADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3) = [SADVANCE \u32ADVANCE \d3(C+RADVANCE \u32ADVANCE \d3B) + (pFADVANCE \d1oADVANCE \u1ADVANCE \u32ADVANCE \d3)ADVANCE \u32ADVANCE \d3]/LpADVANCE \u32ADVANCE \d3 S = Scan rate C = Total integrated peak count R = Ratio of scan time to background counting time B = Total background count Lp = Lorentz-polarization factor p = p-factor (4) Standard deviation of an observation of unit weight: [Sw(|FADVANCE \d1oADVANCE \u1|-|FADVANCE \d1cADVANCE \u1|)ADVANCE \u32ADVANCE \d3/(NADVANCE \d1oADVANCE \u1-NADVANCE \d1vADVANCE \u1)]ADVANCE \u31/2ADVANCE \d3 where NADVANCE \d1oADVANCE \u1 = number of observations NADVANCE \d1vADVANCE \u1 = number of variables (5) Cromer, D. T. & Waber, J. T.; "International Tables for X-ray Crystallography", Vol. IV, The Kynoch Press, Birmingham, England, Table 2.2 A (1974). (6) Ibers, J. A. & Hamilton, W. C.; Acta Crystallogr., 17, 781 (1964). (7) Creagh, D. C. & McAuley, W.J .; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.6.8, pages 219-222 (1992). (8) Creagh, D. C. & Hubbell, J.H..; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.4.3, pages 200-206 (1992). (9) teXsan: Crystal Structure Analysis Package, Molecular Structure Corporation (1985 & 1992). EXPEREMENTAL DETAILS A. Crystal Data Empirical Formula CADVANCE \d335ADVANCE \u3HADVANCE \d338ADVANCE \u3OADVANCE \d37ADVANCE \u3BrADVANCE \d32ADVANCE \u3 Formula Weight 730.49 Crystal Color, Habit colorless, needle Crystal Dimensions 0.05 X 0.05 X 0.16 mm Crystal System orthorhombic Lattice Type Primitive Lattice Parameters a = 7.0834(3) b = 12.7467(4) c = 36.377(1) V = 3284.4(2) ADVANCE \u33ADVANCE \d3 Space Group P2ADVANCE \d31ADVANCE \u32ADVANCE \d31ADVANCE \u32ADVANCE \d31ADVANCE \u3 (#19) Z value 4 DADVANCE \d1calcADVANCE \u1 1.477 g/cmADVANCE \u33ADVANCE \d3 FADVANCE \d1000ADVANCE \u1 1496.00 (MoK) 25.23 cmADVANCE \u3-1ADVANCE \d3 B. Intensity Measurements Diffractometer Nonius KappaCCD Radiation MoK ( = 0.71069 ) graphite monochromated Take-off Angle 2.8ADVANCE \u3oADVANCE \d3 Crystal to Detector Distance 50 mm Temperature -90.0ADVANCE \u3oADVANCE \d3C Scan Rate 81s/frame Scan Width 0.9ADVANCE \u3oADVANCE \d3/frame 2ADVANCE \d1maxADVANCE \u1 50.1ADVANCE \u3oADVANCE \d3 No. of Reflections Measured Total: 5842 Unique: 3378 (RADVANCE \d1intADVANCE \u1 = 0.112) Corrections Lorentz-polarization Secondary Extinction (coefficient: 6.99826e-08) Absorption: SORTAV C. Structure Solution and Refinement Structure Solution Direct Methods (SIR92) Refinement Full-matrix least-squares Function Minimized  w (|Fo| - |Fc|)ADVANCE \u32ADVANCE \d3 Least Squares Weights 1/ ADVANCE \u32ADVANCE \d3(Fo) p-factor 0.0200 Anomalous Dispersion All non-hydrogen atoms No. Observations (I>3.00(I)) 1514 No. Variables 397 Reflection/Parameter Ratio 3.81 Residuals: R; Rw 0.040; 0.034 Goodness of Fit Indicator 1.34 Max Shift/Error in Final Cycle 0.00 Maximum peak in Final Diff. Map 0.34 eADVANCE \u3-ADVANCE \d3/ADVANCE \u33ADVANCE \d3 Minimum peak in Final Diff. Map -0.38 eADVANCE \u3-ADVANCE \d3/ADVANCE \u33ADVANCE \d3 Atomic coordinates and BADVANCE \d1isoADVANCE \u1/BADVANCE \d1eqADVANCE \u1 atom x y z BADVANCE \d1eqADVANCE \u1 ----------------------------------------------------------------------------------------- Br(1) -0.4058(2) -0.09229(8) 0.59808(3) 4.37(3) Br(2) 0.5498(3) 0.03313(10) 0.49628(3) 8.26(5) O(1) 0.0951(9) 0.3186(4) 0.6682(1) 2.0(1) O(2) 0.339(1) 0.2107(5) 0.6535(2) 3.7(2) O(3) 0.2547(9) 0.4174(5) 0.6115(2) 2.4(2) O(4) 0.568(1) 0.4444(5) 0.6178(2) 3.5(2) O(5) 0.375(1) 0.6719(5) 0.5804(2) 3.6(2) O(6) 0.1633(9) 0.7095(5) 0.5361(2) 3.3(2) O(7) 0.1976(10) 0.6703(5) 0.7125(2) 3.0(2) C(1) 0.194(1) 0.4397(7) 0.7154(2) 2.1(2) C(2) 0.233(1) 0.4022(7) 0.6763(2) 2.1(2) C(3) 0.214(1) 0.4815(7) 0.6438(2) 1.9(3) C(4) 0.020(1) 0.5342(7) 0.6361(2) 1.9(2) C(5) -0.006(1) 0.6371(7) 0.6609(2) 1.6(2) C(6) 0.084(2) 0.6141(7) 0.6976(2) 1.8(3) C(7) 0.023(1) 0.5107(7) 0.7141(2) 1.5(2) C(8) 0.172(2) 0.2295(8) 0.6551(3) 2.4(3) C(9) 0.026(2) 0.1538(8) 0.6420(3) 2.2(3) C(10) -0.162(2) 0.1634(8) 0.6508(3) 2.9(3) C(11) -0.292(1) 0.0895(9) 0.6373(3) 3.3(3) C(12) -0.227(2) 0.0095(8) 0.6158(2) 2.5(3) C(13) -0.042(2) -0.0006(7) 0.6062(3) 2.8(3) C(14) 0.082(2) 0.0705(8) 0.6204(3) 3.3(3) C(15) 0.439(2) 0.3999(8) 0.6034(3) 2.4(3) C(16) 0.463(2) 0.3162(8) 0.5752(2) 2.5(3) C(17) 0.309(2) 0.2644(8) 0.5610(3) 3.9(3) C(18) 0.333(2) 0.180(1) 0.5379(3) 5.0(4) C(19) 0.511(3) 0.1499(9) 0.5277(3) 4.9(4) C(20) 0.667(2) 0.199(1) 0.5412(3) 6.4(5) C(21) 0.644(2) 0.2863(9) 0.5651(3) 4.0(4) C(22) 0.002(1) 0.5785(6) 0.5970(2) 2.2(2) C(23) 0.053(1) 0.6966(6) 0.5983(2) 1.9(2) C(24) 0.099(2) 0.7189(6) 0.6389(2) 2.0(2) C(25) 0.211(2) 0.7281(8) 0.5728(3) 2.8(3) C(26) 0.468(2) 0.6527(8) 0.5460(3) 4.8(3) C(27) 0.343(2) 0.7065(8) 0.5178(2) 4.0(3) C(28) -0.218(2) 0.6633(7) 0.6693(2) 2.4(3) C(29) -0.337(1) 0.5869(7) 0.6923(2) 1.8(2) C(30) -0.294(1) 0.5786(7) 0.7336(2) 2.0(2) C(31) -0.103(2) 0.5366(7) 0.7465(2) 2.3(2) C(32) -0.233(1) 0.7739(6) 0.6865(2) 3.5(3) C(33) -0.280(2) 0.4734(7) 0.7533(2) 2.3(3) C(34) -0.350(1) 0.4731(7) 0.7927(2) 3.5(3) C(35) -0.313(1) 0.3690(8) 0.7343(2) 3.0(3) H(1) 0.2998 0.4773 0.7246 2.4670 H(2) 0.1691 0.3813 0.7309 2.4670 H(3) 0.3562 0.3727 0.6756 2.5762 H(4) 0.3077 0.5342 0.6462 2.3383 H(5) -0.0790 0.4859 0.6408 2.2444 H(6) -0.0581 0.4800 0.6963 1.7760 H(7) -0.2040 0.2197 0.6658 3.5054 H(8) -0.4221 0.0951 0.6430 3.9384 H(9) -0.0004 -0.0550 0.5902 3.3720 H(10) 0.2122 0.0624 0.6152 4.0002 H(11) 0.1850 0.2868 0.5670 4.7119 H(12) 0.2272 0.1424 0.5290 5.9753 H(13) 0.7897 0.1760 0.5347 7.6458 H(14) 0.7510 0.3236 0.5740 4.8455 H(15) -0.1234 0.5699 0.5885 2.6213 H(16) 0.0867 0.5428 0.5810 2.6213 H(17) -0.0564 0.7356 0.5918 2.2817 H(18) 0.2306 0.7132 0.6431 2.4223 H(19) 0.0572 0.7872 0.6455 2.4223 H(20) 0.2356 0.8008 0.5759 3.3312 H(21) 0.4754 0.5795 0.5413 5.7604 H(22) 0.5908 0.6821 0.5460 5.7604 H(23) 0.3871 0.7751 0.5125 4.8360 H(24) 0.3361 0.6669 0.4957 4.8360 H(25) -0.2786 0.6678 0.6461 2.8602 H(26) -0.3205 0.5189 0.6821 2.1550 H(27) -0.4649 0.6076 0.6899 2.1550 H(28) -0.3435 0.6342 0.7481 2.4168 H(29) -0.0456 0.5698 0.7671 2.8144 H(30) -0.2227 0.8254 0.6678 4.1554 H(31) -0.3517 0.7808 0.6985 4.1554 H(32) -0.1346 0.7833 0.7039 4.1554 H(33) -0.4233 0.5343 0.7970 4.1477 H(34) -0.2452 0.4723 0.8090 4.1477 H(35) -0.4254 0.4126 0.7968 4.1477 H(36) -0.2561 0.3145 0.7482 3.6318 H(37) -0.2578 0.3708 0.7104 3.6318 H(38) -0.4444 0.3566 0.7322 3.6318 Supplementary Material for Wood et al. Progress Towards the Total Synthesis of Ingenol: the Construction of PAGE  PAGE 21 Supplementary material for Wood et al. 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CS ChemDraw DrawingChemDraw Interchange FormatChemDraw.Document.4.59qCompObj ~ObjInfo CONTENTSy_1046023002!mA. 愭愭VjCD0100ChemDraw 4.5KMicrosoft Word - C:\Yew W6 Folders\Wayne\organic letters\Ingenol data.doc53 2  B7 $$$$xf  `  xg'dd'`Arial 200Cs_3X3_f (99% yield)&p|iM}r  7ڑQQV  8fMff      d dyf d?01' jL dY V ]01  fKT01  fKE  V<01&                    G b01 9M^  Jo      j4  xZ3"  `OMe|7uM"|6ghi+l jlhkhi  @cM)# ! `Og%_&f,!  $ "rD% #&S.& $ %' %$( &~;) '$(* (E+ )(*, *3yL4 2 `O }MIuJ|MP- +,. ,Z@Y/ -,.0 .3ye1 /.02 0je3 102m5 3@d01U<BK6 4j7 5@d01d=>^8 6V01H>?9 7fK&01I?@: 8fK; 9V01TAB< :56= ;67> <78? =89@ >9:A ?:;B @5;C AG01HEIGD B93E CCDF DJ G ECFH F8CI G9CJ H3jZK I5JL Jx&P N`OMe|Zu|fnop+s qsoropM KJLN Lb3Q O `Of_ffO MJNR PrS Q&ST R;SU S5RV T~W URVX VY WVXZ Xv\ Z `Ozsssz[ Y6Z] [rs^ \7]_ ]3}&` ^]_a _f3b `_ac abe c `Hf_Mf3d b7cOle  CompObj ~ObjInfoCONTENTSVjCD0100ChemDraw 4.5KMicrosoft Word - C:\Yew W6 Folders\Wayne\organic letters\Ingenol data.docfnWl2  B7 $$$$xf  `  xg'dd'`Arial (85% yield)2+4 10 mol% 4"s"f  8T͘MT  9&TC3MfC3TMHf $01&  + $015/ Z01  01   M  01%                   Z01   Z 3      *ڂ  9! `OMe<څ6p=ghi+l jlhkhi  Z#w"   `O3'3tf tf'3{ # !2f$ "}% # $& $#' %&?3( &#') 'ZHM* (')+ )M7- + `O&;Z4MZ;, *+. ,2/ -.0 .=1 /.02 0G3 1024 2Z#6 4 `H3'Zf f'͸5 34m7 5'801dAJ_8 6'fR01X=T`9 7U01G=>: 8M01H>?; 9>< :501R@A= ;89> <9:? =:;@ >;<A ?7<B @ Z01GDHFC A3WD BBCE Cf hF DBEG E9BH F:BI G--J H7IK I3<f,O M`OMe @08?/nop+s qsoropL JIKM Kf&3"P N `O@*s#fs*%N LIMQ O'R P<QS Q5ZVT R8SU S@MV TSUW Uf&aY W `H@*]s#^s*fcX V8WZ X@>[ YUZ\ Z55] [Z\^ \Z#F_ ]7^` ^8^a _&Fc a `OB3MC3Ib `^ad b7\e c    & &_1046023052!mA. 愭愭Ole CompObj~ObjInfo !mA. CS ChemDraw DrawingChemDraw Interchange FormatChemDraw.Document.4.59q !mA. CS ChemDraw DrawingChemDraw Interchange FormatChemDraw.Document.4.59qCONTENTSW_1046023120"!mA. 愭V'愭Ole CompObj ~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~VjCD0100ChemDraw 4.5KMicrosoft Word - C:\Yew W6 Folders\Wayne\organic letters\Ingenol data.doc3'&̓2  B7 $$$$xf  `  xg'dd'`Arialg &017 6 @s01. 1  &01$ ( 01  s01  s 01             01    s   Z &f' %`OH+  f  3      ! "  !# !M & $ `H&  $ "#( &!- +@@/ - `H ff . ,-0 .@2 0`OHsfff+1 /06 47 5% #    ) 'LAH 3M3* ((95% yield)3 MfM+ ) 9@$fQ3Q$V, *10#&$fh3 1M4 2M.5 334i8 6F01eBK`9 73`01Y>Ua: 8c01H>?; 9Z01I?@< :L= ;C01SAB> <9:? =:;@ >;<A ?<=B @8=C Ah01HEIGD BeE CCDF DvG ECFH F:CI G;CJ HM;K I8JL JM M:P N`OMe&> M)=jkl+o moknklM KJLN L0Q O `OZ,-3O MJNR Pf5S Q=RT R &dU S9TV TZW UTVX VnZ X `HZkMl3qY W9X[ YL\ ZV[] [ C^ \[]_ ]sS` ^8_a _9_b `@Sd b `OfPfQWc a_be c8] f dc  Rv&WordMicrosoft Word  YCourier New- @Times New Roman-Y&_.  - "-Y^   &&-  !-vC (@ @ @@@@@`@```@@@@ @ @ @ @@ @ @ ` @` ` ` @ @ @ @ @@@@@ @@ @ @ @@@@@@@@@@`@@`@`@`@@@@@@@@@@@@@@@@@@@@@`@``` `@ ` ` `@`@@`@`@```@```````@````@````@````@```@ @ @@@@@`@```@@@@@ @ @@@@@`@```@@@@@ @ @@@@@`@```@@@@@ @ @@@@@`@```@@@@&&&%%MSEPS Preamble [Softek v3.6] /pp_save save def /showpage {} def /s_rebeko 66 dict def s_rebeko begin /pict_box_x1 54 def /pict_box_y1 110 def /pict_box_x2 477 def /pict_box_y2 591 def /scale_the_picture false def /pp_clip false def /CB { { /pp_cy exch def /pp_cx exch def /pp_cht exch def /pp_cwd exch def } stopped not { /pp_clip true def } if } def /B { { /pict_y1 exch def /pict_x1 exch def /pict_y2 exch def /pict_x2 exch def } stopped not { /scale_the_picture true def } if } def - "-  &%pp_clip { pp_cx pp_cy moveto pp_cwd 0 rlineto 0 pp_cht rlineto pp_cwd neg 0 rlineto clip newpath } if scale_the_picture { /pict_y2 pict_y2 pict_y1 add def /pict_x2 pict_x2 pict_x1 add def /scale_x pict_x2 pict_x1 sub pict_box_x2 pict_box_x1 sub div def /scale_y pict_y2 pict_y1 sub pict_box_y1 pict_box_y2 sub div def /pict_kx pict_x1 scale_x pict_box_x1 mul sub def /pict_ky pict_y1 scale_y pict_box_y2 mul sub def pict_kx pict_ky translate scale_x scale_y scale } if end &%%!PS-Adobe-3.0 EPSF-3.0 %%Title: (ortep.pdf) %%Version: 1 2 %%CreationDate: (D:20010312145506) %%DocumentData: Clean7Bit %%BoundingBox: 54 110 477 591 %%Pages: 0 %%DocumentProcessColors: Black %%DocumentSuppliedResources: %%+ procset (Adobe Acrobat - PDF operators) 1.2 0 %%EndComments 54 110 moveto 477 110 lineto 477 591 lineto 54 591 lineto closepath clip newpath %%BeginProlog %%EndProlog %%BeginSetup /currentpacking where{pop currentpacking true setpacking}if %%BeginResource: procset pdfvars %%Copyright: Copyright 1987-1999 Adobe Systems Incorporated. All Rights Reserved. %%Version: 4.0 1 %%Title: definition of dictionary of variables used by PDF & PDFText procsets userdict /PDF 150 dict put userdict /PDFVars 86 dict dup begin put /_save 0 def /_cshow 0 def /InitAll 0 def /TermAll 0 def /DocInitAll 0 def /DocTermAll 0 def /_lp /none def /_doClip 0 def /sfc 0 def /_sfcs 0 def /_sfc 0 def /ssc 0 def /_sscs 0 def /_ssc 0 def /_fcs 0 def /_scs 0 def /_fp 0 def /_sp 0 def /AGM_MAX_CS_COMPONENTS 10 def /_fillColors [ 0 1 AGM_MAX_CS_COMPONENTS { array } for ] def /_strokeColors [ 0 1 AGM_MAX_CS_COMPONENTS { array } for ] def /_fc null def /_sc null def /DefaultGray [/DeviceGray] def /DefaultRGB [/DeviceRGB] def /DefaultCMYK [/DeviceCMYK] def /_inT false def /_tr -1 def /_rise 0 def /_ax 0 def /_cx 0 def /_ld 0 def /_tm matrix def /_ctm matrix def /_mtx matrix def /_hy (-) def /_fScl 0 def /_hs 1 def /_pdfEncodings 2 array def /_baselineadj 0 def /_fTzero false def /_Tj 0 def /_italMtx [1 0 .212557 1 0 0] def /_italMtx_WMode1 [1 -.212557 0 1 0 0] def /_italMtxType0 [1 0 .1062785 1 0 0] def /_italMtx_WMode1Type0 [1 -.1062785 0 1 0 0] def /_basefont 0 def /_basefonto 0 def /_pdf_oldCIDInit null def /_pdf_FontDirectory 30 dict def /_categories 10 dict def /_sa? true def /_op? false def /_OP? false def /_opmode 0 def /_ColorSep5044? false def /_tmpcolr? [] def /_tmpop? {} def /_processColors 0 def /_defaulttransfer currenttransfer def /_defaultflatness currentflat def /_defaulthalftone null def /_defaultcolortransfer null def /_defaultblackgeneration null def /_defaultundercolorremoval null def /_defaultcolortransfer null def end %%EndResource PDFVars begin PDF begin %%BeginResource: procset pdfutil %%Copyright: Copyright 1993-1999 Adobe Systems Incorporated. All Rights Reserved. %%Version: 4.0 1 %%Title: Basic utilities used by other PDF procsets /bd {bind def} bind def /ld {load def} bd /dd { PDFVars 3 1 roll put } bd /xdd { exch dd } bd /Level2? systemdict /languagelevel known { systemdict /languagelevel get 2 ge } { false } ifelse def /Level3? systemdict /languagelevel known {systemdict /languagelevel get 3 eq } { false } ifelse def /getifknown { 2 copy known { get true } { pop pop false } ifelse } bd /here { currentdict exch getifknown } bd /isdefined? { where { pop true } { false } ifelse } bd /StartLoad { dup dup not { /_save save dd } if } bd /EndLoad { if not { _save restore } if } bd %%EndResource %%BeginResource: l2compat %%Copyright: Copyright 1987-1993 Adobe Systems Incorporated. All Rights Reserved. /cshow isdefined? not StartLoad { /cshow { exch /_cshow xdd { 0 0 _cshow exec } forall } bd } EndLoad /setcmykcolor isdefined? not StartLoad { /setcmykcolor { 1 sub 4 1 roll 3 { 3 index add neg dup 0 lt { pop 0 } if 3 1 roll } repeat setrgbcolor pop } bd } EndLoad /rectclip isdefined? not StartLoad { /re 0 def /rectclip { newpath re clip newpath } bd } EndLoad /execform isdefined? not StartLoad { /execform { gsave dup begin Matrix concat BBox aload pop exch 3 index sub exch 2 index sub rectclip PaintProc end grestore } def } EndLoad /sethalftone isdefined? not StartLoad { /sethalftone { begin HalftoneType 1 eq { Frequency Angle /SpotFunction load setscreen } if end } bd } EndLoad %%EndResource %%BeginResource: procset pdf %%Version: 4.0 1 %%Copyright: Copyright 1998-1999 Adobe Systems Incorporated. All Rights Reserved. %%Ti&%tle: General operators for PDF, common to all Language Levels. [/b/B/b*/B*/BDC/BI/BMC/BT/BX/c/cm/cs/CS/d/d0/d1/Do/DP/EI/EMC/ET/EX/f/f*/g/G/gs /h/i/j/J/k/K/l/m/M/MP/n/q/Q/re/rg/RG/ri/s/S/sc/SC/scn/SCN/sg/Tc/Td/TD/Tf/Tj/TJ /TL/Tm/Tr/Ts/Tw/Tz/T*/v/w/W/W*/y/'/" /applyInterpFunc/applystitchFunc/domainClip/EF/encodeInput/gsDI/ilp/icl /initgs/int/limit/PS/rangeClip/RC/rf/makePat ] {null def} bind forall /v { currentpoint 6 2 roll c } bd /y { 2 copy c } bd /h/closepath ld /d/setdash ld /j/setlinejoin ld /J/setlinecap ld /M/setmiterlimit ld /w/setlinewidth ld /i { dup 0 eq { pop _defaultflatness } if setflat } bd /gsDI { begin /Font here { aload pop Tf } if /LW here { w } if /LC here { J } if /LJ here { j } if /ML here { M } if /D here { aload pop d } if end } bd /ilp { /_lp /none dd } bd /sfc { _lp /fill ne { _sfcs _sfc /_lp /fill dd } if } dd /ssc { _lp /stroke ne { _sscs _ssc /_lp /stroke dd } if } dd /icl { /_doClip 0 dd } bd /W { /_doClip 1 dd } bd /W* { /_doClip 2 dd } bd /n { {{} {clip} {eoclip}} _doClip get exec icl newpath } bd /s { h S } bd /B { q f Q S } bd /B* { q f* Q S } bd /b { h B } bd /b* { h B* } bd /q/save ld /Q { restore ilp } bd /GetCSFamily { dup type /arraytype eq {0 get} if } bd /GetCompsDict 11 dict begin /DeviceGray { pop 1 } bd /DeviceRGB { pop 3 } bd /DeviceCMYK { pop 4 } bd /CIEBasedA { pop 1 } bd /CIEBasedABC { pop 3 } bd /CIEBasedDEF { pop 3 } bd /CIEBasedDEFG { pop 4 } bd /DeviceN { 1 get length } bd /Separation { pop 1 } bd /Indexed { pop 1 } bd /Pattern { pop 0 } bd currentdict end def /GetComps { GetCompsDict 1 index GetCSFamily get exec } bd /cs { dup _fcs eq { pop } { dup /_fcs xdd GetComps _fillColors exch get /_fc xdd /_fp null dd } ifelse } bd /CS { dup _scs eq { pop } { dup /_scs xdd GetComps _strokeColors exch get /_sc xdd /_sp null dd } ifelse } bd /sc { _fc astore pop ilp } bd /SC { _sc astore pop ilp } bd /g { DefaultGray cs sc } bd /rg { DefaultRGB cs sc } bd /k { DefaultCMYK cs sc } bd /G { DefaultGray CS SC } bd /RG { DefaultRGB CS SC } bd /K { DefaultCMYK CS SC } bd /cm { _mtx astore concat } bd /re { 4 2 roll m 1 index 0 rlineto 0 exch rlineto neg 0 rlineto h } bd /RC/rectclip ld /EF/execform ld /PS { cvx exec } bd /initgs { /DefaultGray [/DeviceGray] dd /DefaultRGB [/DeviceRGB] dd /DefaultCMYK [/DeviceCMYK] dd 0 g 0 G [] 0 d 0 j 0 J 10 M 1 w true setSA /_op? false dd /_OP? false dd /_opmode 0 dd /_defaulttransfer load 5 dict begin settransfer end 0 i newpath } bd /int { dup 2 index sub 3 index 5 index sub div 6 -2 roll sub mul exch pop add exch pop } bd /limit { dup 2 index le { exch } if pop dup 2 index ge { exch } if pop } bd /domainClip { Domain aload pop 3 2 roll limit } bd /applyInterpFunc { 0 1 DimOut 1 sub { dup C0 exch get exch dup C1 exch get exch 3 1 roll 1 index sub 3 index N exp mul add exch currentdict /Range_lo known { dup Range_lo exch get exch Range_hi exch get 3 2 roll limit } { pop } ifelse exch } for pop } bd /encodeInput { NumParts 1 sub 0 1 2 index { dup Bounds exch get 2 index gt { exit } { dup 3 index eq { exit } { pop } ifelse } ifelse } for 3 2 roll pop dup Bounds exch get exch dup 1 add Bounds exch get exch 2 mul dup Encode exch get exch 1 add Encode exch get int } bd /rangeClip { exch dup Range_lo exch get exch Range_hi exch get 3 2 roll limit } bd /applyStitchFunc { Functions exch get exec currentdict /Range_lo known { 0 1 DimOut 1 sub { DimOut 1 add -1 roll rangeClip } for } if } bind def %%EndResource %%BeginResource: procset sep_ops %%Version: 4.0 1 %%Copyright: Copyright 1987-1999 Adobe Systems Incorporated. All Rights Reserved. %%Title: Support for Separations in Level 1, following the conventions of Tech Note 5044 userdict /sep_ops 50 dict dup begin put /bdef {bind def} bind def /xdef {exch def} bdef /colorimagebuffer { 0 1 2 index length 1 sub { dup 2 index exch get 255 exch sub 2 index 3 1 r&%oll put } for } bdef /addprocs { [ 3 1 roll /exec load dup 3 1 roll ] cvx } bdef /L1? { systemdict /languagelevel known { systemdict /languagelevel get 2 lt }{ true } ifelse } bdef /colorexists { statusdict /processcolors known { statusdict /processcolors get exec }{ /deviceinfo where { pop deviceinfo /Colors known { deviceinfo /Colors get statusdict /processcolors { deviceinfo /Colors known { deviceinfo /Colors get }{ 1 } ifelse } put }{ 1 } ifelse }{ 1 } ifelse } ifelse 1 gt } bdef /colorplate colorexists { 0 } { 5 } ifelse def /negativecolorplate false def /setcmykcolor where { pop gsave 1 0 0 0 setcmykcolor systemdict /currentgray get exec 1 exch sub 0 1 0 0 setcmykcolor systemdict /currentgray get exec 1 exch sub 0 0 1 0 setcmykcolor systemdict /currentgray get exec 1 exch sub 0 0 0 1 setcmykcolor systemdict /currentgray get exec 1 exch sub 4 {4 copy} repeat grestore 1 dict begin /foureq { 4 index eq 8 1 roll 4 index eq 8 1 roll 4 index eq 8 1 roll 4 index eq 8 1 roll pop pop pop pop and and and } def 1 0 0 0 foureq {/colorplate 1 store} if 0 1 0 0 foureq {/colorplate 2 store} if 0 0 1 0 foureq {/colorplate 3 store} if 0 0 0 1 foureq {/colorplate 4 store} if 0 0 0 0 foureq {/colorplate 6 store} if end } if 0 systemdict /currenttransfer get exec exec 1 systemdict /currenttransfer get exec exec 2 copy eq { /colorplate 6 store pop /negativecolorplate exch 0.5 lt store } { gt /negativecolorplate exch store } ifelse /findcmykcustomcolor where { pop } { /findcmykcustomcolor { [ 6 1 roll ] readonly } bdef } ifelse /setoverprint where { pop }{ /setoverprint { pop } bdef } ifelse /setcustomcolor where { pop }{ L1? { /setcustomcolor { exch aload pop pop 4 { 4 index mul 4 1 roll } repeat 5 -1 roll pop setcmykcolor } bdef }{ /setcustomcolor { exch [ exch /Separation exch dup 4 get exch /DeviceCMYK exch 0 4 getinterval [ exch /dup load exch cvx {mul exch dup} /forall load /pop load dup] cvx ] setcolorspace setcolor } bdef } ifelse } ifelse /ik 0 def /iy 0 def /im 0 def /ic 0 def /imagetint { ic .3 mul im .59 mul iy .11 mul ik add add add dup 1 gt {pop 1} if } bdef /setcmykcolor where { pop }{ /setcmykcolor { /ik xdef /iy xdef /im xdef /ic xdef imagetint 1 exch sub setgray } bdef } ifelse /customcolorimage where { pop }{ L1? { /customcolorimage{ gsave colorexists { aload pop pop /ik xdef /iy xdef /im xdef /ic xdef currentcolortransfer {ik mul ik sub 1 add} addprocs 4 1 roll {iy mul iy sub 1 add} addprocs 4 1 roll {im mul im sub 1 add} addprocs 4 1 roll {ic mul ic sub 1 add} addprocs 4 1 roll setcolortransfer /magentabuf 0 string def /yellowbuf 0 string def /blackbuf 0 string def { colorimagebuffer dup length magentabuf length ne { dup length dup dup /magentabuf exch string def /yellowbuf exch string def /blackbuf exch string def } if dup magentabuf copy yellowbuf copy blackbuf copy pop } addprocs {magentabuf}{yellowbuf}{blackbuf} true 4 colorimage }{ aload pop pop /ik xdef /iy xdef /im xdef /ic xdef /tint imagetint def currenttransfer {tint mul 1 tint sub add} addprocs settransfer image } ifelse grestore } bdef }{ /customcolorimage { gsave [ exch /Separation exch dup 4 get exch /DeviceCMYK exch 0 4 getinterval [ exch /dup load exch cvx {mul exch dup} /forall load /pop load dup] cvx ] setcolorspace 10 dict begin /ImageType 1 def /DataSource exch def /ImageMatrix exch def /BitsPerComponent exch def /Height exch def /Width exch def /Decode [1 0] def currentdict end image grestore } bdef } ifelse } ifelse /setseparationgray where { pop }{ L1? { /setseparationgray { 1 exch sub dup dup dup setcmykcolor } bdef }{ /setseparationgray { [/Separation /All /DeviceCMYK {dup dup dup}] setcolorspace 1 exch sub setcolor } bdef } ifelse } ifelse /separationimage where { pop } { /separationimage { gsave 1 1 1 1 (All) findcmykcustomcolor customcolorimage grestore } bdef } ifelse currentdict readonly pop end&% %%EndResource %%BeginResource: procset pdflev15044 %%Version: 4.0 1 %%Copyright: Copyright 1987-1990 Adobe Systems Incorporated. All Rights Reserved. %%LanguageLevel: 1 %%Title: PDF operators, Level 1, with emulated separations (TN 5044) /_ColorSep5044? true dd currentscreen dup type /dicttype eq { /_defaulthalftone xdd pop pop } { 5 dict begin 1 [/HalftoneType /SpotFunction /Angle /Frequency ] { exch def } forall /_defaulthalftone currentdict end dd } ifelse /currentcolortransfer where { pop /_defaultcolortransfer [ currentcolortransfer ] dd } { /setcolortransfer { settransfer pop pop pop } bd /_defaultcolortransfer [currenttransfer dup dup dup] dd } ifelse /initialize { sep_ops begin 50 dict begin _defaulthalftone sethalftone } bd /terminate { end end } bd /pl { transform 0.25 sub round 0.25 add exch 0.25 sub round 0.25 add exch itransform } bd /m { _sa? { pl } if moveto } bd /l { _sa? { pl } if lineto } bd /c { _sa? { pl } if curveto } bd /setSA { /_sa? xdd } bd /AlmostFull? { dup maxlength exch length sub 2 le } bd /Expand { 1 index maxlength mul cvi dict dup begin exch { def } forall end } bd /xput { 3 2 roll dup 3 index known not { dup AlmostFull? { 1.5 Expand } if } if dup 4 2 roll put } bd /defineRes { _categories 1 index known not { /_categories _categories 2 index 10 dict xput store } if _categories exch 2 copy get 5 -1 roll 4 index xput put } bd /findRes { _categories exch get exch get } bd /ri/pop ld /L1setcolor { aload length dup 0 eq { pop .5 setgray } { dup 1 eq { pop setgray } { 3 eq { setrgbcolor } { setcmykcolor } ifelse } ifelse } ifelse } bind dd /_sfcs { } dd /_sscs { } dd /scn { sc } bd /SCN { SC } bd /rf {re f} bd /concattransferfuncs { [ 3 1 roll /exec load exch /exec load ] cvx } bd /concatandsettransfer { /_defaulttransfer load concattransferfuncs settransfer } bd /concatandsetcolortransfer { colorplate 0 eq { _defaultcolortransfer aload pop 8 -1 roll 5 -1 roll concattransferfuncs 7 1 roll 6 -1 roll 4 -1 roll concattransferfuncs 5 1 roll 4 -1 roll 3 -1 roll concattransferfuncs 3 1 roll concattransferfuncs setcolortransfer } if colorplate 1 ge colorplate 4 le and { 4 colorplate sub index 4 { exch pop } repeat concatandsettransfer } if colorplate 5 ge { 0 index 4 { exch pop } repeat concatandsettransfer } if } bd /tn5044sethalftone { begin HalftoneType 5 eq { [/Default /Cyan /Magenta /Yellow /Black /Default /Default /Default] colorplate get here not { /Default here not { currentdict } if } if } { currentdict } ifelse end begin /TransferFunction here { concatandsettransfer currentdict dup length dict begin { 1 index /TransferFunction ne { def } { pop pop } ifelse } forall currentdict end } { currentdict } ifelse end sethalftone } bd /gs { begin /SA here { /_sa? xdd } if /OP here { /_OP? xdd } if /op here { /_op? xdd } { /OP here { /_op? xdd } if } ifelse /TR here { dup xcheck { concatandsettransfer } { aload pop concatandsetcolortransfer } ifelse } if /HT here { tn5044sethalftone } if /FL here { i } if currentdict gsDI end } bd /_sfc { _fp null eq { _fcs type /arraytype eq {_fcs 0 get /Separation eq { _fcs 1 get /All eq { _fc aload pop 1 exch sub /setseparationgray where pop begin setseparationgray end } { 1 _fcs 3 get exec _fcs 1 get /findcmykcustomcolor where pop begin findcmykcustomcolor end _fc aload pop /setcustomcolor where pop begin setcustomcolor end } ifelse } { _fc L1setcolor } ifelse } { _fc L1setcolor } ifelse } { _fc L1setcolor } ifelse _op? setoverprint } bind dd /_ssc { _sp null eq { _scs type /arraytype eq {_scs 0 get /Separation eq { _scs 1 get /All eq { _sc aload pop 1 exch sub /setseparationgray where pop begin setseparationgray end } { 1 _scs 3 get exec _scs 1 get /findcmykcustomcolor where pop begin findcmykcustomcolor end _sc aload pop /setcustomcolor where pop begin setcustomcolor end } ifelse } { _sc L1setcolor } ifelse } { _sc&% L1setcolor } ifelse } { _sc L1setcolor } ifelse _OP? setoverprint } bind dd /f { { { sfc fill } {gsave sfc fill grestore clip newpath icl ilp} {gsave sfc fill grestore eoclip newpath icl ilp} } _doClip get exec } bd /f* { { { sfc eofill } {gsave sfc eofill grestore clip newpath icl ilp} {gsave sfc eofill grestore eoclip newpath icl ilp} } _doClip get exec } bd /S { { { ssc stroke } {gsave ssc stroke grestore clip newpath icl ilp} {gsave ssc stroke grestore eoclip newpath icl ilp} } _doClip get exec } bd /rf {re f} bd %%EndResource currentdict readonly pop end end /currentpacking where {pop setpacking}if PDFVars/DocInitAll{[]{/docinitialize get exec}forall }put PDFVars/InitAll{[PDF]{/initialize get exec}forall initgs}put PDFVars/TermAll{[PDF]{/terminate get exec}forall}put PDFVars begin PDF begin PDFVars/DocInitAll get exec PDFVars/InitAll get exec PDFVars/TermAll get exec end end %%EndSetup PDFVars begin PDF begin PDFVars/InitAll get exec 54 110 424 481 re W n /N23 16 dict dup begin /SA false def /TR {}def /SM 0.02 def end /ExtGState defineRes pop 0 G 0 J 0 j 0.39999 w 10 M []0 d /N23 /ExtGState findRes gs 1 i 268.60001 430.5 m 268.7 430.5 l 268.7 430.5 m 268.89999 430.60001 l 268.89999 430.60001 m 269.3 430.7 l 269.3 430.7 m 269.8 430.8 l 269.8 430.8 m 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CS ChemDraw DrawingChemDraw Interchange FormatChemDraw.Document.4.59q !mA. CS ChemDraw DrawingChemDraw Interchange FormatChemDraw.Document.4.59qObjInfoqzCONTENTS\k_1046004941mht!mA. H愭H愭Ole {      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~                           ! " # $ % & ' ( ) * + , - . / 0 1 2 3 4 5 6 7 8 9 : ; < = > ? @ A B C D E F G H I J K L M N O P Q R S T U V W X Y Z [ \ ] ^ _ ` a b c d e f g h i j k l m n o p q r s t u v w x y z { | } ~  VjCD0100ChemDraw 4.5#Microsoft Word - Ingenol data.doc[`2  B7 $$$$xf  `  xxpg(dd'`Arial, Z01$  Z  01  01  Z Z01&             01       Zz! `CO2Me3}M]fM}-./01+6 26.3./4.0501 "   `OZfM Z  # ! `OZ͡     $ " % #3Zt& $%7' %f( &ff) ''(* (17ffff3 + )c 0c 1&WordMicrosoft Word  =Courier New- @Times New Roman-=&>.  - "-==   &&-  !-C (#@ @ @@@@@`@```@@@@ @ @ @ @@ @ @ ` @` ` ` @ @ @ @ @@@@@ @@ @ @ @@@@@@@@@@`@@`@`@`@@@@@@@@@@@@@@@@@@@@@`@``` `@ ` ` `@`@@`@`@```@```````@````@````@````@```@ @ @@@@@`@```@@@@@ @ @@@@@`@```@@@@@ @ @@@@@`@```@@@@@ @ @@@@@`@```@@@@&&&%%MSEPS Preamble [Softek v3.6] /pp_save save def /showpage {} def /s_rebeko 66 dict def s_rebeko begin /pict_box_x1 15 def /pict_box_y1 202 def /pict_box_x2 506 def /pict_box_y2 487 def /scale_the_picture false def /pp_clip false def /CB { { /pp_cy exch def /pp_cx exch def /pp_cht exch def /pp_cwd exch def } stopped not { /pp_clip true def } if } def /B { { /pict_y1 exch def /pict_x1 exch def /pict_y2 exch def /pict_x2 exch def } stopped not { /scale_the_picture true def } if } def - "-  &%pp_clip { pp_cx pp_cy moveto pp_cwd 0 rlineto 0 pp_cht rlineto pp_cwd neg 0 rlineto clip newpath } if scale_the_picture { /pict_y2 pict_y2 pict_y1 add def /pict_x2 pict_x2 pict_x1 add def /scale_x pict_x2 pict_x1 sub pict_box_x2 pict_box_x1 sub div def /scale_y pict_y2 pict_y1 sub pict_box_y1 pict_box_y2 sub div def /pict_kx pict_x1 scale_x pict_box_x1 mul sub def /pict_ky pict_y1 scale_y pict_box_y2 mul sub def pict_kx pict_ky translate scale_x scale_y scale } if end &%%!PS-Adobe-3.0 EPSF-3.0 %%Title: (ortep.pdf) %%Version: 1 2 %%CreationDate: (D:20010312190659) %%DocumentData: Clean7Bit %%BoundingBox: 15 202 506 487 %%Pages: 0 %%DocumentProcessColors: Black %%DocumentSuppliedResources: %%+ procset (Adobe Acrobat - PDF operators) 1.2 0 %%EndComments 15 202 moveto 506 202 lineto 506 487 lineto 15 487 lineto closepath clip newpath %%BeginProlog %%EndProlog %%BeginSetup /currentpacking where{pop currentpacking true setpacking}if %%BeginResource: procset pdfvars %%Copyright: Copyright 1987-1999 Adobe Systems Incorporated. All Rights Reserved. %%Version: 4.0 1 %%Title: definition of dictionary of variables used by PDF & PDFText procsets userdict /PDF 150 dict put userdict /PDFVars 86 dict dup begin put /_save 0 def /_cshow 0 def /InitAll 0 def /TermAll 0 def /DocInitAll 0 def /DocTermAll 0 def /_lp /none def /_doClip 0 def /sfc 0 def /_sfcs 0 def /_sfc 0 def /ssc 0 def /_sscs 0 def /_ssc 0 def /_fcs 0 def /_scs 0 def /_fp 0 def /_sp 0 def /AGM_MAX_CS_COMPONENTS 10 def /_fillColors [ 0 1 AGM_MAX_CS_COMPONENTS { array } for ] def /_strokeColors [ 0 1 AGM_MAX_CS_COMPONENTS { array } for ] def /_fc null def /_sc null def /DefaultGray [/DeviceGray] def /DefaultRGB [/DeviceRGB] def /DefaultCMYK [/DeviceCMYK] def /_inT false def /_tr -1 def /_rise 0 def /_ax 0 def /_cx 0 def /_ld 0 def /_tm matrix def /_ctm matrix def /_mtx matrix def /_hy (-) def /_fScl 0 def /_hs 1 def /_pdfEncodings 2 array def /_baselineadj 0 def /_fTzero false def /_Tj 0 def /_italMtx [1 0 .212557 1 0 0] def /_italMtx_WMode1 [1 -.212557 0 1 0 0] def /_italMtxType0 [1 0 .1062785 1 0 0] def /_italMtx_WMode1Type0 [1 -.1062785 0 1 0 0] def /_basefont 0 def /_basefonto 0 def /_pdf_oldCIDInit null def /_pdf_FontDirectory 30 dict def /_categories 10 dict def /_sa? true def /_op? false def /_OP? false def /_opmode 0 def /_ColorSep5044? false def /_tmpcolr? [] def /_tmpop? {} def /_processColors 0 def /_defaulttransfer currenttransfer def /_defaultflatness currentflat def /_defaulthalftone null def /_defaultcolortransfer null def /_defaultblackgeneration null def /_defaultundercolorremoval null def /_defaultcolortransfer null def end %%EndResource PDFVars begin PDF begin %%BeginResource: procset pdfutil %%Copyright: Copyright 1993-1999 Adobe Systems Incorporated. All Rights Reserved. %%Version: 4.0 1 %%Title: Basic utilities used by other PDF procsets /bd {bind def} bind def /ld {load def} bd /dd { PDFVars 3 1 roll put } bd /xdd { exch dd } bd /Level2? systemdict /languagelevel known { systemdict /languagelevel get 2 ge } { false } ifelse def /Level3? systemdict /languagelevel known {systemdict /languagelevel get 3 eq } { false } ifelse def /getifknown { 2 copy known { get true } { pop pop false } ifelse } bd /here { currentdict exch getifknown } bd /isdefined? { where { pop true } { false } ifelse } bd /StartLoad { dup dup not { /_save save dd } if } bd /EndLoad { if not { _save restore } if } bd %%EndResource %%BeginResource: l2compat %%Copyright: Copyright 1987-1993 Adobe Systems Incorporated. All Rights Reserved. /cshow isdefined? not StartLoad { /cshow { exch /_cshow xdd { 0 0 _cshow exec } forall } bd } EndLoad /setcmykcolor isdefined? not StartLoad { /setcmykcolor { 1 sub 4 1 roll 3 { 3 index add neg dup 0 lt { pop 0 } if 3 1 roll } repeat setrgbcolor pop } bd } EndLoad /rectclip isdefined? not StartLoad { /re 0 def /rectclip { newpath re clip newpath } bd } EndLoad /execform isdefined? not StartLoad { /execform { gsave dup begin Matrix concat BBox aload pop exch 3 index sub exch 2 index sub rectclip PaintProc end grestore } def } EndLoad /sethalftone isdefined? not StartLoad { /sethalftone { begin HalftoneType 1 eq { Frequency Angle /SpotFunction load setscreen } if end } bd } EndLoad %%EndResource %%BeginResource: procset pdf %%Version: 4.0 1 %%Copyright: Copyright 1998-1999 Adobe Systems Incorporated. All Rights Reserved. %%Ti&%tle: General operators for PDF, common to all Language Levels. [/b/B/b*/B*/BDC/BI/BMC/BT/BX/c/cm/cs/CS/d/d0/d1/Do/DP/EI/EMC/ET/EX/f/f*/g/G/gs /h/i/j/J/k/K/l/m/M/MP/n/q/Q/re/rg/RG/ri/s/S/sc/SC/scn/SCN/sg/Tc/Td/TD/Tf/Tj/TJ /TL/Tm/Tr/Ts/Tw/Tz/T*/v/w/W/W*/y/'/" /applyInterpFunc/applystitchFunc/domainClip/EF/encodeInput/gsDI/ilp/icl /initgs/int/limit/PS/rangeClip/RC/rf/makePat ] {null def} bind forall /v { currentpoint 6 2 roll c } bd /y { 2 copy c } bd /h/closepath ld /d/setdash ld /j/setlinejoin ld /J/setlinecap ld /M/setmiterlimit ld /w/setlinewidth ld /i { dup 0 eq { pop _defaultflatness } if setflat } bd /gsDI { begin /Font here { aload pop Tf } if /LW here { w } if /LC here { J } if /LJ here { j } if /ML here { M } if /D here { aload pop d } if end } bd /ilp { /_lp /none dd } bd /sfc { _lp /fill ne { _sfcs _sfc /_lp /fill dd } if } dd /ssc { _lp /stroke ne { _sscs _ssc /_lp /stroke dd } if } dd /icl { /_doClip 0 dd } bd /W { /_doClip 1 dd } bd /W* { /_doClip 2 dd } bd /n { {{} {clip} {eoclip}} _doClip get exec icl newpath } bd /s { h S } bd /B { q f Q S } bd /B* { q f* Q S } bd /b { h B } bd /b* { h B* } bd /q/save ld /Q { restore ilp } bd /GetCSFamily { dup type /arraytype eq {0 get} if } bd /GetCompsDict 11 dict begin /DeviceGray { pop 1 } bd /DeviceRGB { pop 3 } bd /DeviceCMYK { pop 4 } bd /CIEBasedA { pop 1 } bd /CIEBasedABC { pop 3 } bd /CIEBasedDEF { pop 3 } bd /CIEBasedDEFG { pop 4 } bd /DeviceN { 1 get length } bd /Separation { pop 1 } bd /Indexed { pop 1 } bd /Pattern { pop 0 } bd currentdict end def /GetComps { GetCompsDict 1 index GetCSFamily get exec } bd /cs { dup _fcs eq { pop } { dup /_fcs xdd GetComps _fillColors exch get /_fc xdd /_fp null dd } ifelse } bd /CS { dup _scs eq { pop } { dup /_scs xdd GetComps _strokeColors exch get /_sc xdd /_sp null dd } ifelse } bd /sc { _fc astore pop ilp } bd /SC { _sc astore pop ilp } bd /g { DefaultGray cs sc } bd /rg { DefaultRGB cs sc } bd /k { DefaultCMYK cs sc } bd /G { DefaultGray CS SC } bd /RG { DefaultRGB CS SC } bd /K { DefaultCMYK CS SC } bd /cm { _mtx astore concat } bd /re { 4 2 roll m 1 index 0 rlineto 0 exch rlineto neg 0 rlineto h } bd /RC/rectclip ld /EF/execform ld /PS { cvx exec } bd /initgs { /DefaultGray [/DeviceGray] dd /DefaultRGB [/DeviceRGB] dd /DefaultCMYK [/DeviceCMYK] dd 0 g 0 G [] 0 d 0 j 0 J 10 M 1 w true setSA /_op? false dd /_OP? false dd /_opmode 0 dd /_defaulttransfer load 5 dict begin settransfer end 0 i newpath } bd /int { dup 2 index sub 3 index 5 index sub div 6 -2 roll sub mul exch pop add exch pop } bd /limit { dup 2 index le { exch } if pop dup 2 index ge { exch } if pop } bd /domainClip { Domain aload pop 3 2 roll limit } bd /applyInterpFunc { 0 1 DimOut 1 sub { dup C0 exch get exch dup C1 exch get exch 3 1 roll 1 index sub 3 index N exp mul add exch currentdict /Range_lo known { dup Range_lo exch get exch Range_hi exch get 3 2 roll limit } { pop } ifelse exch } for pop } bd /encodeInput { NumParts 1 sub 0 1 2 index { dup Bounds exch get 2 index gt { exit } { dup 3 index eq { exit } { pop } ifelse } ifelse } for 3 2 roll pop dup Bounds exch get exch dup 1 add Bounds exch get exch 2 mul dup Encode exch get exch 1 add Encode exch get int } bd /rangeClip { exch dup Range_lo exch get exch Range_hi exch get 3 2 roll limit } bd /applyStitchFunc { Functions exch get exec currentdict /Range_lo known { 0 1 DimOut 1 sub { DimOut 1 add -1 roll rangeClip } for } if } bind def %%EndResource %%BeginResource: procset sep_ops %%Version: 4.0 1 %%Copyright: Copyright 1987-1999 Adobe Systems Incorporated. All Rights Reserved. %%Title: Support for Separations in Level 1, following the conventions of Tech Note 5044 userdict /sep_ops 50 dict dup begin put /bdef {bind def} bind def /xdef {exch def} bdef /colorimagebuffer { 0 1 2 index length 1 sub { dup 2 index exch get 255 exch sub 2 index 3 1 r&%oll put } for } bdef /addprocs { [ 3 1 roll /exec load dup 3 1 roll ] cvx } bdef /L1? { systemdict /languagelevel known { systemdict /languagelevel get 2 lt }{ true } ifelse } bdef /colorexists { statusdict /processcolors known { statusdict /processcolors get exec }{ /deviceinfo where { pop deviceinfo /Colors known { deviceinfo /Colors get statusdict /processcolors { deviceinfo /Colors known { deviceinfo /Colors get }{ 1 } ifelse } put }{ 1 } ifelse }{ 1 } ifelse } ifelse 1 gt } bdef /colorplate colorexists { 0 } { 5 } ifelse def /negativecolorplate false def /setcmykcolor where { pop gsave 1 0 0 0 setcmykcolor systemdict /currentgray get exec 1 exch sub 0 1 0 0 setcmykcolor systemdict /currentgray get exec 1 exch sub 0 0 1 0 setcmykcolor systemdict /currentgray get exec 1 exch sub 0 0 0 1 setcmykcolor systemdict /currentgray get exec 1 exch sub 4 {4 copy} repeat grestore 1 dict begin /foureq { 4 index eq 8 1 roll 4 index eq 8 1 roll 4 index eq 8 1 roll 4 index eq 8 1 roll pop pop pop pop and and and } def 1 0 0 0 foureq {/colorplate 1 store} if 0 1 0 0 foureq {/colorplate 2 store} if 0 0 1 0 foureq {/colorplate 3 store} if 0 0 0 1 foureq {/colorplate 4 store} if 0 0 0 0 foureq {/colorplate 6 store} if end } if 0 systemdict /currenttransfer get exec exec 1 systemdict /currenttransfer get exec exec 2 copy eq { /colorplate 6 store pop /negativecolorplate exch 0.5 lt store } { gt /negativecolorplate exch store } ifelse /findcmykcustomcolor where { pop } { /findcmykcustomcolor { [ 6 1 roll ] readonly } bdef } ifelse /setoverprint where { pop }{ /setoverprint { pop } bdef } ifelse /setcustomcolor where { pop }{ L1? { /setcustomcolor { exch aload pop pop 4 { 4 index mul 4 1 roll } repeat 5 -1 roll pop setcmykcolor } bdef }{ /setcustomcolor { exch [ exch /Separation exch dup 4 get exch /DeviceCMYK exch 0 4 getinterval [ exch /dup load exch cvx {mul exch dup} /forall load /pop load dup] cvx ] setcolorspace setcolor } bdef } ifelse } ifelse /ik 0 def /iy 0 def /im 0 def /ic 0 def /imagetint { ic .3 mul im .59 mul iy .11 mul ik add add add dup 1 gt {pop 1} if } bdef /setcmykcolor where { pop }{ /setcmykcolor { /ik xdef /iy xdef /im xdef /ic xdef imagetint 1 exch sub setgray } bdef } ifelse /customcolorimage where { pop }{ L1? { /customcolorimage{ gsave colorexists { aload pop pop /ik xdef /iy xdef /im xdef /ic xdef currentcolortransfer {ik mul ik sub 1 add} addprocs 4 1 roll {iy mul iy sub 1 add} addprocs 4 1 roll {im mul im sub 1 add} addprocs 4 1 roll {ic mul ic sub 1 add} addprocs 4 1 roll setcolortransfer /magentabuf 0 string def /yellowbuf 0 string def /blackbuf 0 string def { colorimagebuffer dup length magentabuf length ne { dup length dup dup /magentabuf exch string def /yellowbuf exch string def /blackbuf exch string def } if dup magentabuf copy yellowbuf copy blackbuf copy pop } addprocs {magentabuf}{yellowbuf}{blackbuf} true 4 colorimage }{ aload pop pop /ik xdef /iy xdef /im xdef /ic xdef /tint imagetint def currenttransfer {tint mul 1 tint sub add} addprocs settransfer image } ifelse grestore } bdef }{ /customcolorimage { gsave [ exch /Separation exch dup 4 get exch /DeviceCMYK exch 0 4 getinterval [ exch /dup load exch cvx {mul exch dup} /forall load /pop load dup] cvx ] setcolorspace 10 dict begin /ImageType 1 def /DataSource exch def /ImageMatrix exch def /BitsPerComponent exch def /Height exch def /Width exch def /Decode [1 0] def currentdict end image grestore } bdef } ifelse } ifelse /setseparationgray where { pop }{ L1? { /setseparationgray { 1 exch sub dup dup dup setcmykcolor } bdef }{ /setseparationgray { [/Separation /All /DeviceCMYK {dup dup dup}] setcolorspace 1 exch sub setcolor } bdef } ifelse } ifelse /separationimage where { pop } { /separationimage { gsave 1 1 1 1 (All) findcmykcustomcolor customcolorimage grestore } bdef } ifelse currentdict readonly pop end&% %%EndResource %%BeginResource: procset pdflev15044 %%Version: 4.0 1 %%Copyright: Copyright 1987-1990 Adobe Systems Incorporated. All Rights Reserved. %%LanguageLevel: 1 %%Title: PDF operators, Level 1, with emulated separations (TN 5044) /_ColorSep5044? true dd currentscreen dup type /dicttype eq { /_defaulthalftone xdd pop pop } { 5 dict begin 1 [/HalftoneType /SpotFunction /Angle /Frequency ] { exch def } forall /_defaulthalftone currentdict end dd } ifelse /currentcolortransfer where { pop /_defaultcolortransfer [ currentcolortransfer ] dd } { /setcolortransfer { settransfer pop pop pop } bd /_defaultcolortransfer [currenttransfer dup dup dup] dd } ifelse /initialize { sep_ops begin 50 dict begin _defaulthalftone sethalftone } bd /terminate { end end } bd /pl { transform 0.25 sub round 0.25 add exch 0.25 sub round 0.25 add exch itransform } bd /m { _sa? { pl } if moveto } bd /l { _sa? { pl } if lineto } bd /c { _sa? { pl } if curveto } bd /setSA { /_sa? xdd } bd /AlmostFull? { dup maxlength exch length sub 2 le } bd /Expand { 1 index maxlength mul cvi dict dup begin exch { def } forall end } bd /xput { 3 2 roll dup 3 index known not { dup AlmostFull? { 1.5 Expand } if } if dup 4 2 roll put } bd /defineRes { _categories 1 index known not { /_categories _categories 2 index 10 dict xput store } if _categories exch 2 copy get 5 -1 roll 4 index xput put } bd /findRes { _categories exch get exch get } bd /ri/pop ld /L1setcolor { aload length dup 0 eq { pop .5 setgray } { dup 1 eq { pop setgray } { 3 eq { setrgbcolor } { setcmykcolor } ifelse } ifelse } ifelse } bind dd /_sfcs { } dd /_sscs { } dd /scn { sc } bd /SCN { SC } bd /rf {re f} bd /concattransferfuncs { [ 3 1 roll /exec load exch /exec load ] cvx } bd /concatandsettransfer { /_defaulttransfer load concattransferfuncs settransfer } bd /concatandsetcolortransfer { colorplate 0 eq { _defaultcolortransfer aload pop 8 -1 roll 5 -1 roll concattransferfuncs 7 1 roll 6 -1 roll 4 -1 roll concattransferfuncs 5 1 roll 4 -1 roll 3 -1 roll concattransferfuncs 3 1 roll concattransferfuncs setcolortransfer } if colorplate 1 ge colorplate 4 le and { 4 colorplate sub index 4 { exch pop } repeat concatandsettransfer } if colorplate 5 ge { 0 index 4 { exch pop } repeat concatandsettransfer } if } bd /tn5044sethalftone { begin HalftoneType 5 eq { [/Default /Cyan /Magenta /Yellow /Black /Default /Default /Default] colorplate get here not { /Default here not { currentdict } if } if } { currentdict } ifelse end begin /TransferFunction here { concatandsettransfer currentdict dup length dict begin { 1 index /TransferFunction ne { def } { pop pop } ifelse } forall currentdict end } { currentdict } ifelse end sethalftone } bd /gs { begin /SA here { /_sa? xdd } if /OP here { /_OP? xdd } if /op here { /_op? xdd } { /OP here { /_op? xdd } if } ifelse /TR here { dup xcheck { concatandsettransfer } { aload pop concatandsetcolortransfer } ifelse } if /HT here { tn5044sethalftone } if /FL here { i } if currentdict gsDI end } bd /_sfc { _fp null eq { _fcs type /arraytype eq {_fcs 0 get /Separation eq { _fcs 1 get /All eq { _fc aload pop 1 exch sub /setseparationgray where pop begin setseparationgray end } { 1 _fcs 3 get exec _fcs 1 get /findcmykcustomcolor where pop begin findcmykcustomcolor end _fc aload pop /setcustomcolor where pop begin setcustomcolor end } ifelse } { _fc L1setcolor } ifelse } { _fc L1setcolor } ifelse } { _fc L1setcolor } ifelse _op? setoverprint } bind dd /_ssc { _sp null eq { _scs type /arraytype eq {_scs 0 get /Separation eq { _scs 1 get /All eq { _sc aload pop 1 exch sub /setseparationgray where pop begin setseparationgray end } { 1 _scs 3 get exec _scs 1 get /findcmykcustomcolor where pop begin findcmykcustomcolor end _sc aload pop /setcustomcolor where pop begin setcustomcolor end } ifelse } { _sc L1setcolor } ifelse } { _sc&% L1setcolor } ifelse } { _sc L1setcolor } ifelse _OP? setoverprint } bind dd /f { { { sfc fill } {gsave sfc fill grestore clip newpath icl ilp} {gsave sfc fill grestore eoclip newpath icl ilp} } _doClip get exec } bd /f* { { { sfc eofill } {gsave sfc eofill grestore clip newpath icl ilp} {gsave sfc eofill grestore eoclip newpath icl ilp} } _doClip get exec } bd /S { { { ssc stroke } {gsave ssc stroke grestore clip newpath icl ilp} {gsave ssc stroke grestore eoclip newpath icl ilp} } _doClip get exec } bd /rf {re f} bd %%EndResource currentdict readonly pop end end /currentpacking where {pop setpacking}if PDFVars/DocInitAll{[]{/docinitialize get exec}forall }put PDFVars/InitAll{[PDF]{/initialize get exec}forall initgs}put PDFVars/TermAll{[PDF]{/terminate get exec}forall}put PDFVars begin PDF begin PDFVars/DocInitAll get exec PDFVars/InitAll get exec PDFVars/TermAll get exec end end %%EndSetup PDFVars begin PDF begin PDFVars/InitAll get exec 15 202 491 285 re W n /N23 16 dict dup begin /SA false def /TR {}def /SM 0.02 def end /ExtGState defineRes pop 0 G 0 J 0 j 0.39999 w 10 M []0 d /N23 /ExtGState findRes gs 1 i 115.5 351.39999 m 116.10001 352.39999 l 116.10001 352.39999 m 116.7 353.3 l 116.7 353.3 m 117.5 354.2 l 117.5 354.2 m 118.39999 354.89999 l 118.39999 354.89999 m 120.39999 356.10001 l 120.39999 356.10001 m 121.5 356.5 l 121.5 356.5 m 122.7 356.8 l 122.7 356.8 m 124 357 l 124 357 m 125.3 357.10001 l 125.3 357.10001 m 126.60001 357.10001 l 126.60001 357.10001 m 127.89999 356.89999 l 127.89999 356.89999 m 129.2 356.60001 l 129.2 356.60001 m 130.3 356.3 l 136.5 352.7 m 137.5 351.8 l 137.5 351.8 m 138.3 350.8 l 138.3 350.8 m 139.10001 349.7 l 139.10001 349.7 m 139.8 348.60001 l 139.8 348.60001 m 140.39999 347.39999 l 140.39999 347.39999 m 140.89999 346.2 l 140.89999 346.2 m 141.2 345 l 141.2 345 m 141.39999 343.8 l 141.39999 343.8 m 141.5 342.60001 l 141.5 342.60001 m 141.39999 341.39999 l 141.39999 341.39999 m 141.2 340.3 l 141.2 340.3 m 140.89999 339.2 l 140.89999 339.2 m 140.5 338.10001 l 135.2 352.10001 m 128 344.8 l 118.8 355.2 m 129.39999 346.2 l 130.7 347.5 m 120.60001 356.2 l 122.8 356.8 m 132.10001 348.89999 l 133.39999 350.3 m 125.39999 357.10001 l 128.89999 356.7 m 130 355.7 l 132 354.10001 m 134.8 351.7 l 137.8 334.39999 m 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C42)rgD ?>`BR<X=LZij`_yobgc(,{\͙eeHQ0)G*{nY1ܩ.=#bL| Hϸ腖;]] ~lSec#S$dW0NK^0U~@ ˯jXeã^ W!RJH'TDBTF`u(FU$, >vV!F#B4B &qvUhdZǧ:dNѓ%K%jۙ~gS\uMRVd $ڢR!Ch Mܚ LO6>Xa$C$Fms)ڬ0Z: Nu "FJº43J3T#I$y@=( he9%5٭,kfE~MV=AnM?E/`l>CRQ(=?=" d+шkCompObjsu|~ObjInfov~CONTENTSZ o_1046024716y!mA. H愭H愭                           ! " # $ % & ' ( ) * + , - . / 0 1 2 3 4 5 6 7 8 9 : ; < = > ? @ A B C D E F G H I J K L M N O P Q R S T U V W X Y Z [ \ ] ^ _ ` a b c d e f g h i j k l m n o p q r s t u v w x y z { | } ~                            ! " # $ % & ' ( ) * + , - . / 0 1 2 3 4 5 6 7 8 9 : ; < = > ? @ A B C D E F G H I J K L M N O P Q R S T U V W X Y Z [ \ ] ^ _ ` a b c d e f g h i j k l m n o p q r s t u v w x y z { | } ~                           ! " # $ % & ' ( ) * + , - . / 0 1 2 3 4 5 6 7 8 9 : ; < = > ? @ A B C D E F G H I J K L M N O P Q S T U V W X Y Z [ \ ] ^ _ ` a b c d e f g h i j k l m n o p q r s t u v w x y z { | } ~  VjCD0100ChemDraw 4.5KMicrosoft Word - C:\Yew W6 Folders\Wayne\organic letters\Ingenol data.docR F2^  B7 $$$$xf  `  xogg(dd'`Arial:  f   c d |s&WordMicrosoft Word  Courier New- @Times New Roman-&.  - "-   &&-  !-sC (<@ @ @@@@@`@```@@@@ @ @ @ @@ @ @ ` @` ` ` @ @ @ @ @@@@@ @@ @ @ @@@@@@@@@@`@@`@`@`@@@@@@@@@@@@@@@@@@@@@`@``` `@ ` ` `@`@@`@`@```@```````@````@````@````@```@ @ @@@@@`@```@@@@@ @ @@@@@`@```@@@@@ @ @@@@@`@```@@@@@ @ @@@@@`@```@@@@&&&%%MSEPS Preamble [Softek v3.6] /pp_save save def /showpage {} def /s_rebeko 66 dict def s_rebeko begin /pict_box_x1 22 def /pict_box_y1 150 def /pict_box_x2 503 def /pict_box_y2 541 def /scale_the_picture false def /pp_clip false def /CB { { /pp_cy exch def /pp_cx exch def /pp_cht exch def /pp_cwd exch def } stopped not { /pp_clip true def } if } def /B { { /pict_y1 exch def /pict_x1 exch def /pict_y2 exch def /pict_x2 exch def } stopped not { /scale_the_picture true def } if } def - "-  &%pp_clip { pp_cx pp_cy moveto pp_cwd 0 rlineto 0 pp_cht rlineto pp_cwd neg 0 rlineto clip newpath } if scale_the_picture { /pict_y2 pict_y2 pict_y1 add def /pict_x2 pict_x2 pict_x1 add def /scale_x pict_x2 pict_x1 sub pict_box_x2 pict_box_x1 sub div def /scale_y pict_y2 pict_y1 sub pict_box_y1 pict_box_y2 sub div def /pict_kx pict_x1 scale_x pict_box_x1 mul sub def /pict_ky pict_y1 scale_y pict_box_y2 mul sub def pict_kx pict_ky translate scale_x scale_y scale } if end &%%!PS-Adobe-3.0 EPSF-3.0 %%Title: (ortep.pdf) %%Version: 1 2 %%CreationDate: (D:20010312191309) %%DocumentData: Clean7Bit %%BoundingBox: 22 150 503 541 %%Pages: 0 %%DocumentProcessColors: Black %%DocumentSuppliedResources: %%+ procset (Adobe Acrobat - PDF operators) 1.2 0 %%EndComments 22 150 moveto 503 150 lineto 503 541 lineto 22 541 lineto closepath clip newpath %%BeginProlog %%EndProlog %%BeginSetup /currentpacking where{pop currentpacking true setpacking}if %%BeginResource: procset pdfvars %%Copyright: Copyright 1987-1999 Adobe Systems Incorporated. All Rights Reserved. %%Version: 4.0 1 %%Title: definition of dictionary of variables used by PDF & PDFText procsets userdict /PDF 150 dict put userdict /PDFVars 86 dict dup begin put /_save 0 def /_cshow 0 def /InitAll 0 def /TermAll 0 def /DocInitAll 0 def /DocTermAll 0 def /_lp /none def /_doClip 0 def /sfc 0 def /_sfcs 0 def /_sfc 0 def /ssc 0 def /_sscs 0 def /_ssc 0 def /_fcs 0 def /_scs 0 def /_fp 0 def /_sp 0 def /AGM_MAX_CS_COMPONENTS 10 def /_fillColors [ 0 1 AGM_MAX_CS_COMPONENTS { array } for ] def /_strokeColors [ 0 1 AGM_MAX_CS_COMPONENTS { array } for ] def /_fc null def /_sc null def /DefaultGray [/DeviceGray] def /DefaultRGB [/DeviceRGB] def /DefaultCMYK [/DeviceCMYK] def /_inT false def /_tr -1 def /_rise 0 def /_ax 0 def /_cx 0 def /_ld 0 def /_tm matrix def /_ctm matrix def /_mtx matrix def /_hy (-) def /_fScl 0 def /_hs 1 def /_pdfEncodings 2 array def /_baselineadj 0 def /_fTzero false def /_Tj 0 def /_italMtx [1 0 .212557 1 0 0] def /_italMtx_WMode1 [1 -.212557 0 1 0 0] def /_italMtxType0 [1 0 .1062785 1 0 0] def /_italMtx_WMode1Type0 [1 -.1062785 0 1 0 0] def /_basefont 0 def /_basefonto 0 def /_pdf_oldCIDInit null def /_pdf_FontDirectory 30 dict def /_categories 10 dict def /_sa? true def /_op? false def /_OP? false def /_opmode 0 def /_ColorSep5044? false def /_tmpcolr? [] def /_tmpop? {} def /_processColors 0 def /_defaulttransfer currenttransfer def /_defaultflatness currentflat def /_defaulthalftone null def /_defaultcolortransfer null def /_defaultblackgeneration null def /_defaultundercolorremoval null def /_defaultcolortransfer null def end %%EndResource PDFVars begin PDF begin %%BeginResource: procset pdfutil %%Copyright: Copyright 1993-1999 Adobe Systems Incorporated. All Rights Reserved. %%Version: 4.0 1 %%Title: Basic utilities used by other PDF procsets /bd {bind def} bind def /ld {load def} bd /dd { PDFVars 3 1 roll put } bd /xdd { exch dd } bd /Level2? systemdict /languagelevel known { systemdict /languagelevel get 2 ge } { false } ifelse def /Level3? systemdict /languagelevel known {systemdict /languagelevel get 3 eq } { false } ifelse def /getifknown { 2 copy known { get true } { pop pop false } ifelse } bd /here { currentdict exch getifknown } bd /isdefined? { where { pop true } { false } ifelse } bd /StartLoad { dup dup not { /_save save dd } if } bd /EndLoad { if not { _save restore } if } bd %%EndResource %%BeginResource: l2compat %%Copyright: Copyright 1987-1993 Adobe Systems Incorporated. All Rights Reserved. /cshow isdefined? not StartLoad { /cshow { exch /_cshow xdd { 0 0 _cshow exec } forall } bd } EndLoad /setcmykcolor isdefined? not StartLoad { /setcmykcolor { 1 sub 4 1 roll 3 { 3 index add neg dup 0 lt { pop 0 } if 3 1 roll } repeat setrgbcolor pop } bd } EndLoad /rectclip isdefined? not StartLoad { /re 0 def /rectclip { newpath re clip newpath } bd } EndLoad /execform isdefined? not StartLoad { /execform { gsave dup begin Matrix concat BBox aload pop exch 3 index sub exch 2 index sub rectclip PaintProc end grestore } def } EndLoad /sethalftone isdefined? not StartLoad { /sethalftone { begin HalftoneType 1 eq { Frequency Angle /SpotFunction load setscreen } if end } bd } EndLoad %%EndResource %%BeginResource: procset pdf %%Version: 4.0 1 %%Copyright: Copyright 1998-1999 Adobe Systems Incorporated. All Rights Reserved. %%Ti&%tle: General operators for PDF, common to all Language Levels. [/b/B/b*/B*/BDC/BI/BMC/BT/BX/c/cm/cs/CS/d/d0/d1/Do/DP/EI/EMC/ET/EX/f/f*/g/G/gs /h/i/j/J/k/K/l/m/M/MP/n/q/Q/re/rg/RG/ri/s/S/sc/SC/scn/SCN/sg/Tc/Td/TD/Tf/Tj/TJ /TL/Tm/Tr/Ts/Tw/Tz/T*/v/w/W/W*/y/'/" /applyInterpFunc/applystitchFunc/domainClip/EF/encodeInput/gsDI/ilp/icl /initgs/int/limit/PS/rangeClip/RC/rf/makePat ] {null def} bind forall /v { currentpoint 6 2 roll c } bd /y { 2 copy c } bd /h/closepath ld /d/setdash ld /j/setlinejoin ld /J/setlinecap ld /M/setmiterlimit ld /w/setlinewidth ld /i { dup 0 eq { pop _defaultflatness } if setflat } bd /gsDI { begin /Font here { aload pop Tf } if /LW here { w } if /LC here { J } if /LJ here { j } if /ML here { M } if /D here { aload pop d } if end } bd /ilp { /_lp /none dd } bd /sfc { _lp /fill ne { _sfcs _sfc /_lp /fill dd } if } dd /ssc { _lp /stroke ne { _sscs _ssc /_lp /stroke dd } if } dd /icl { /_doClip 0 dd } bd /W { /_doClip 1 dd } bd /W* { /_doClip 2 dd } bd /n { {{} {clip} {eoclip}} _doClip get exec icl newpath } bd /s { h S } bd /B { q f Q S } bd /B* { q f* Q S } bd /b { h B } bd /b* { h B* } bd /q/save ld /Q { restore ilp } bd /GetCSFamily { dup type /arraytype eq {0 get} if } bd /GetCompsDict 11 dict begin /DeviceGray { pop 1 } bd /DeviceRGB { pop 3 } bd /DeviceCMYK { pop 4 } bd /CIEBasedA { pop 1 } bd /CIEBasedABC { pop 3 } bd /CIEBasedDEF { pop 3 } bd /CIEBasedDEFG { pop 4 } bd /DeviceN { 1 get length } bd /Separation { pop 1 } bd /Indexed { pop 1 } bd /Pattern { pop 0 } bd currentdict end def /GetComps { GetCompsDict 1 index GetCSFamily get exec } bd /cs { dup _fcs eq { pop } { dup /_fcs xdd GetComps _fillColors exch get /_fc xdd /_fp null dd } ifelse } bd /CS { dup _scs eq { pop } { dup /_scs xdd GetComps _strokeColors exch get /_sc xdd /_sp null dd } ifelse } bd /sc { _fc astore pop ilp } bd /SC { _sc astore pop ilp } bd /g { DefaultGray cs sc } bd /rg { DefaultRGB cs sc } bd /k { DefaultCMYK cs sc } bd /G { DefaultGray CS SC } bd /RG { DefaultRGB CS SC } bd /K { DefaultCMYK CS SC } bd /cm { _mtx astore concat } bd /re { 4 2 roll m 1 index 0 rlineto 0 exch rlineto neg 0 rlineto h } bd /RC/rectclip ld /EF/execform ld /PS { cvx exec } bd /initgs { /DefaultGray [/DeviceGray] dd /DefaultRGB [/DeviceRGB] dd /DefaultCMYK [/DeviceCMYK] dd 0 g 0 G [] 0 d 0 j 0 J 10 M 1 w true setSA /_op? false dd /_OP? false dd /_opmode 0 dd /_defaulttransfer load 5 dict begin settransfer end 0 i newpath } bd /int { dup 2 index sub 3 index 5 index sub div 6 -2 roll sub mul exch pop add exch pop } bd /limit { dup 2 index le { exch } if pop dup 2 index ge { exch } if pop } bd /domainClip { Domain aload pop 3 2 roll limit } bd /applyInterpFunc { 0 1 DimOut 1 sub { dup C0 exch get exch dup C1 exch get exch 3 1 roll 1 index sub 3 index N exp mul add exch currentdict /Range_lo known { dup Range_lo exch get exch Range_hi exch get 3 2 roll limit } { pop } ifelse exch } for pop } bd /encodeInput { NumParts 1 sub 0 1 2 index { dup Bounds exch get 2 index gt { exit } { dup 3 index eq { exit } { pop } ifelse } ifelse } for 3 2 roll pop dup Bounds exch get exch dup 1 add Bounds exch get exch 2 mul dup Encode exch get exch 1 add Encode exch get int } bd /rangeClip { exch dup Range_lo exch get exch Range_hi exch get 3 2 roll limit } bd /applyStitchFunc { Functions exch get exec currentdict /Range_lo known { 0 1 DimOut 1 sub { DimOut 1 add -1 roll rangeClip } for } if } bind def %%EndResource %%BeginResource: procset sep_ops %%Version: 4.0 1 %%Copyright: Copyright 1987-1999 Adobe Systems Incorporated. All Rights Reserved. %%Title: Support for Separations in Level 1, following the conventions of Tech Note 5044 userdict /sep_ops 50 dict dup begin put /bdef {bind def} bind def /xdef {exch def} bdef /colorimagebuffer { 0 1 2 index length 1 sub { dup 2 index exch get 255 exch sub 2 index 3 1 r&%oll put } for } bdef /addprocs { [ 3 1 roll /exec load dup 3 1 roll ] cvx } bdef /L1? { systemdict /languagelevel known { systemdict /languagelevel get 2 lt }{ true } ifelse } bdef /colorexists { statusdict /processcolors known { statusdict /processcolors get exec }{ /deviceinfo where { pop deviceinfo /Colors known { deviceinfo /Colors get statusdict /processcolors { deviceinfo /Colors known { deviceinfo /Colors get }{ 1 } ifelse } put }{ 1 } ifelse }{ 1 } ifelse } ifelse 1 gt } bdef /colorplate colorexists { 0 } { 5 } ifelse def /negativecolorplate false def /setcmykcolor where { pop gsave 1 0 0 0 setcmykcolor systemdict /currentgray get exec 1 exch sub 0 1 0 0 setcmykcolor systemdict /currentgray get exec 1 exch sub 0 0 1 0 setcmykcolor systemdict /currentgray get exec 1 exch sub 0 0 0 1 setcmykcolor systemdict /currentgray get exec 1 exch sub 4 {4 copy} repeat grestore 1 dict begin /foureq { 4 index eq 8 1 roll 4 index eq 8 1 roll 4 index eq 8 1 roll 4 index eq 8 1 roll pop pop pop pop and and and } def 1 0 0 0 foureq {/colorplate 1 store} if 0 1 0 0 foureq {/colorplate 2 store} if 0 0 1 0 foureq {/colorplate 3 store} if 0 0 0 1 foureq {/colorplate 4 store} if 0 0 0 0 foureq {/colorplate 6 store} if end } if 0 systemdict /currenttransfer get exec exec 1 systemdict /currenttransfer get exec exec 2 copy eq { /colorplate 6 store pop /negativecolorplate exch 0.5 lt store } { gt /negativecolorplate exch store } ifelse /findcmykcustomcolor where { pop } { /findcmykcustomcolor { [ 6 1 roll ] readonly } bdef } ifelse /setoverprint where { pop }{ /setoverprint { pop } bdef } ifelse /setcustomcolor where { pop }{ L1? { /setcustomcolor { exch aload pop pop 4 { 4 index mul 4 1 roll } repeat 5 -1 roll pop setcmykcolor } bdef }{ /setcustomcolor { exch [ exch /Separation exch dup 4 get exch /DeviceCMYK exch 0 4 getinterval [ exch /dup load exch cvx {mul exch dup} /forall load /pop load dup] cvx ] setcolorspace setcolor } bdef } ifelse } ifelse /ik 0 def /iy 0 def /im 0 def /ic 0 def /imagetint { ic .3 mul im .59 mul iy .11 mul ik add add add dup 1 gt {pop 1} if } bdef /setcmykcolor where { pop }{ /setcmykcolor { /ik xdef /iy xdef /im xdef /ic xdef imagetint 1 exch sub setgray } bdef } ifelse /customcolorimage where { pop }{ L1? { /customcolorimage{ gsave colorexists { aload pop pop /ik xdef /iy xdef /im xdef /ic xdef currentcolortransfer {ik mul ik sub 1 add} addprocs 4 1 roll {iy mul iy sub 1 add} addprocs 4 1 roll {im mul im sub 1 add} addprocs 4 1 roll {ic mul ic sub 1 add} addprocs 4 1 roll setcolortransfer /magentabuf 0 string def /yellowbuf 0 string def /blackbuf 0 string def { colorimagebuffer dup length magentabuf length ne { dup length dup dup /magentabuf exch string def /yellowbuf exch string def /blackbuf exch string def } if dup magentabuf copy yellowbuf copy blackbuf copy pop } addprocs {magentabuf}{yellowbuf}{blackbuf} true 4 colorimage }{ aload pop pop /ik xdef /iy xdef /im xdef /ic xdef /tint imagetint def currenttransfer {tint mul 1 tint sub add} addprocs settransfer image } ifelse grestore } bdef }{ /customcolorimage { gsave [ exch /Separation exch dup 4 get exch /DeviceCMYK exch 0 4 getinterval [ exch /dup load exch cvx {mul exch dup} /forall load /pop load dup] cvx ] setcolorspace 10 dict begin /ImageType 1 def /DataSource exch def /ImageMatrix exch def /BitsPerComponent exch def /Height exch def /Width exch def /Decode [1 0] def currentdict end image grestore } bdef } ifelse } ifelse /setseparationgray where { pop }{ L1? { /setseparationgray { 1 exch sub dup dup dup setcmykcolor } bdef }{ /setseparationgray { [/Separation /All /DeviceCMYK {dup dup dup}] setcolorspace 1 exch sub setcolor } bdef } ifelse } ifelse /separationimage where { pop } { /separationimage { gsave 1 1 1 1 (All) findcmykcustomcolor customcolorimage grestore } bdef } ifelse currentdict readonly pop end&% %%EndResource %%BeginResource: procset pdflev15044 %%Version: 4.0 1 %%Copyright: Copyright 1987-1990 Adobe Systems Incorporated. All Rights Reserved. %%LanguageLevel: 1 %%Title: PDF operators, Level 1, with emulated separations (TN 5044) /_ColorSep5044? true dd currentscreen dup type /dicttype eq { /_defaulthalftone xdd pop pop } { 5 dict begin 1 [/HalftoneType /SpotFunction /Angle /Frequency ] { exch def } forall /_defaulthalftone currentdict end dd } ifelse /currentcolortransfer where { pop /_defaultcolortransfer [ currentcolortransfer ] dd } { /setcolortransfer { settransfer pop pop pop } bd /_defaultcolortransfer [currenttransfer dup dup dup] dd } ifelse /initialize { sep_ops begin 50 dict begin _defaulthalftone sethalftone } bd /terminate { end end } bd /pl { transform 0.25 sub round 0.25 add exch 0.25 sub round 0.25 add exch itransform } bd /m { _sa? { pl } if moveto } bd /l { _sa? { pl } if lineto } bd /c { _sa? { pl } if curveto } bd /setSA { /_sa? xdd } bd /AlmostFull? { dup maxlength exch length sub 2 le } bd /Expand { 1 index maxlength mul cvi dict dup begin exch { def } forall end } bd /xput { 3 2 roll dup 3 index known not { dup AlmostFull? { 1.5 Expand } if } if dup 4 2 roll put } bd /defineRes { _categories 1 index known not { /_categories _categories 2 index 10 dict xput store } if _categories exch 2 copy get 5 -1 roll 4 index xput put } bd /findRes { _categories exch get exch get } bd /ri/pop ld /L1setcolor { aload length dup 0 eq { pop .5 setgray } { dup 1 eq { pop setgray } { 3 eq { setrgbcolor } { setcmykcolor } ifelse } ifelse } ifelse } bind dd /_sfcs { } dd /_sscs { } dd /scn { sc } bd /SCN { SC } bd /rf {re f} bd /concattransferfuncs { [ 3 1 roll /exec load exch /exec load ] cvx } bd /concatandsettransfer { /_defaulttransfer load concattransferfuncs settransfer } bd /concatandsetcolortransfer { colorplate 0 eq { _defaultcolortransfer aload pop 8 -1 roll 5 -1 roll concattransferfuncs 7 1 roll 6 -1 roll 4 -1 roll concattransferfuncs 5 1 roll 4 -1 roll 3 -1 roll concattransferfuncs 3 1 roll concattransferfuncs setcolortransfer } if colorplate 1 ge colorplate 4 le and { 4 colorplate sub index 4 { exch pop } repeat concatandsettransfer } if colorplate 5 ge { 0 index 4 { exch pop } repeat concatandsettransfer } if } bd /tn5044sethalftone { begin HalftoneType 5 eq { [/Default /Cyan /Magenta /Yellow /Black /Default /Default /Default] colorplate get here not { /Default here not { currentdict } if } if } { currentdict } ifelse end begin /TransferFunction here { concatandsettransfer currentdict dup length dict begin { 1 index /TransferFunction ne { def } { pop pop } ifelse } forall currentdict end } { currentdict } ifelse end sethalftone } bd /gs { begin /SA here { /_sa? xdd } if /OP here { /_OP? xdd } if /op here { /_op? xdd } { /OP here { /_op? xdd } if } ifelse /TR here { dup xcheck { concatandsettransfer } { aload pop concatandsetcolortransfer } ifelse } if /HT here { tn5044sethalftone } if /FL here { i } if currentdict gsDI end } bd /_sfc { _fp null eq { _fcs type /arraytype eq {_fcs 0 get /Separation eq { _fcs 1 get /All eq { _fc aload pop 1 exch sub /setseparationgray where pop begin setseparationgray end } { 1 _fcs 3 get exec _fcs 1 get /findcmykcustomcolor where pop begin findcmykcustomcolor end _fc aload pop /setcustomcolor where pop begin setcustomcolor end } ifelse } { _fc L1setcolor } ifelse } { _fc L1setcolor } ifelse } { _fc L1setcolor } ifelse _op? setoverprint } bind dd /_ssc { _sp null eq { _scs type /arraytype eq {_scs 0 get /Separation eq { _scs 1 get /All eq { _sc aload pop 1 exch sub /setseparationgray where pop begin setseparationgray end } { 1 _scs 3 get exec _scs 1 get /findcmykcustomcolor where pop begin findcmykcustomcolor end _sc aload pop /setcustomcolor where pop begin setcustomcolor end } ifelse } { _sc L1setcolor } ifelse } { _sc&% L1setcolor } ifelse } { _sc L1setcolor } ifelse _OP? setoverprint } bind dd /f { { { sfc fill } {gsave sfc fill grestore clip newpath icl ilp} {gsave sfc fill grestore eoclip newpath icl ilp} } _doClip get exec } bd /f* { { { sfc eofill } {gsave sfc eofill grestore clip newpath icl ilp} {gsave sfc eofill grestore eoclip newpath icl ilp} } _doClip get exec } bd /S { { { ssc stroke } {gsave ssc stroke grestore clip newpath icl ilp} {gsave ssc stroke grestore eoclip newpath icl ilp} } _doClip get exec } bd /rf {re f} bd %%EndResource currentdict readonly pop end end /currentpacking where {pop setpacking}if PDFVars/DocInitAll{[]{/docinitialize get exec}forall }put PDFVars/InitAll{[PDF]{/initialize get exec}forall initgs}put PDFVars/TermAll{[PDF]{/terminate get exec}forall}put PDFVars begin PDF begin PDFVars/DocInitAll get exec PDFVars/InitAll get exec PDFVars/TermAll get exec end end %%EndSetup PDFVars begin PDF begin PDFVars/InitAll get exec 22 150 482 391 re W n /N23 16 dict dup begin /SA false def /TR {}def /SM 0.02 def end /ExtGState defineRes pop 0 G 0 J 0 j 0.39999 w 10 M []0 d /N23 /ExtGState findRes gs 1 i 89.5 218.7 m 89.3 219 l 89.3 219 m 89.10001 220 l 89.10001 220 m 89 220.60001 l 89 220.60001 m 89.2 222 l 89.2 222 m 89.39999 222.8 l 89.39999 222.8 m 90 224.39999 l 90 224.39999 m 90.39999 225.3 l 90.39999 225.3 m 91.39999 227.10001 l 91.39999 227.10001 m 92.60001 228.89999 l 92.60001 228.89999 m 93.3 229.7 l 93.3 229.7 m 94 230.60001 l 94 230.60001 m 94.7 231.39999 l 94.7 231.39999 m 95.39999 232.10001 l 95.39999 232.10001 m 97 233.5 l 97 233.5 m 97.7 234.10001 l 97.7 234.10001 m 98.5 234.60001 l 98.5 234.60001 m 98.60001 234.60001 l 98.7 234.7 m 99.2 235 l 99.2 235 m 99.89999 235.39999 l 99.89999 235.39999 m 100.60001 235.7 l 100.60001 235.7 m 101.3 235.89999 l 101.3 235.89999 m 101.89999 236 l 101.89999 236 m 102.39999 236.10001 l 102.39999 236.10001 m 103.39999 235.89999 l 103.39999 235.89999 m 103.8 235.60001 l 103 236 m 96.8 227 l 93.2 229.60001 m 97.89999 228.5 l 98.89999 230 m 94.39999 231 l 95.8 232.5 m 99.89999 231.5 l 100.89999 233 m 97.39999 233.8 l 99.3 235.10001 m 102 234.5 l 112.10001 215.7 m 111.89999 215.60001 l 111.89999 215.60001 m 111.60001 215.60001 l 111.60001 215.60001 m 111.10001 215.7 l 111.10001 215.7 m 110.5 216 l 110.5 216 m 109.8 216.3 l 109.8 216.3 m 108.89999 216.7 l 108.89999 216.7 m 107.89999 217.2 l 107.89999 217.2 m 106.89999 217.89999 l 106.89999 217.89999 m 105.7 218.60001 l 105.7 218.60001 m 103.10001 220.2 l 103.10001 220.2 m 101.7 221.2 l 101.7 221.2 m 100.2 222.10001 l 100.2 222.10001 m 98.7 223.2 l 98.7 223.2 m 97.2 224.2 l 97.2 224.2 m 94.2 226.39999 l 94.2 226.39999 m 92.8 227.60001 l 92.8 227.60001 m 91.3 228.7 l 91.3 228.7 m 90 229.8 l 90 229.8 m 88.7 230.8 l 88.7 230.8 m 87.39999 231.89999 l 87.39999 231.89999 m 86.3 232.8 l 86.3 232.8 m 85.3 233.8 l 85.3 233.8 m 84.3 234.60001 l 84.3 234.60001 m 82.8 236.10001 l 82.8 236.10001 m 82.3 236.7 l 82.3 236.7 m 81.89999 237.2 l 81.89999 237.2 m 81.60001 237.7 l 81.60001 237.7 m 81.5 238 l 81.5 238 m 81.60001 238.2 l 92.10001 228.10001 m 96.8 227 l 110.39999 216 m 96 227.10001 l 95.2 227.3 m 109 216.7 l 107.10001 217.7 m 94.5 227.5 l S 93.7 227.7 m 104.5 219.3 l 100.89999 221.7 m 92.89999 227.89999 l 97.89999 239.2 m 99.2 238.5 l 99.2 238.5 m 100.8 237.60001 l 100.8 237.60001 m 102.2 236.60001 l 102.2 236.60001 m 103.7 235.39999 l 103.7 235.39999 m 105 234.3 l 105 234.3 m 106.3 233 l 106.3 233 m 107.5 231.7 l 107.5 231.7 m 108.60001 230.3 l 108.60001 230.3 m 109.60001 228.89999 l 109.60001 228.89999 m 111.2 226.10001 l 111.2 226.10001 m 112.2 223.3 l 112.2 223.3 m 112.5 221.89999 l 112.5 221.89999 m 112.60001 220.60001 l 112.60001 220.60001 m 112.60001 219.39999 l 112.60001 219.39999 m 112.5 218.2 l 112.5 218.2 m 112.10001 217.10001 l 112.10001 217.10001 m 111.7 216.10001 l &%111.7 216.10001 m 111.10001 215.3 l 111.10001 215.3 m 110.3 214.5 l 110.3 214.5 m 109.5 213.8 l 109.5 213.8 m 108.5 213.3 l 108.5 213.3 m 107.39999 212.89999 l 107.39999 212.89999 m 106.2 212.60001 l 106.2 212.60001 m 104.89999 212.5 l 104.89999 212.5 m 103.5 212.5 l 103.5 212.5 m 102.10001 212.7 l 102.10001 212.7 m 100.60001 213 l 111.39999 215.7 m 96.8 227 l 105.3 234 m 99.3 225.10001 l 101.7 223.2 m 107.5 231.7 l 109.5 229.10001 m 104.10001 221.3 l 106.5 219.39999 m 111.10001 226.2 l 112.39999 222.5 m 109 217.5 l 88.2 219.7 m 87.10001 220.7 l 87.10001 220.7 m 85.8 222 l 85.8 222 m 84.7 223.39999 l 84.7 223.39999 m 82.7 226.2 l 82.7 226.2 m 82 227.60001 l 82 227.60001 m 81.3 229.10001 l 81.3 229.10001 m 80.89999 230.5 l 80.89999 230.5 m 80.5 231.8 l 80.5 231.8 m 80.3 234.39999 l 80.3 234.39999 m 80.5 235.60001 l 80.5 235.60001 m 80.8 236.7 l 80.8 236.7 m 81.2 237.7 l 81.2 237.7 m 81.89999 238.60001 l 81.89999 238.60001 m 82.60001 239.39999 l 82.60001 239.39999 m 83.5 240.10001 l 83.5 240.10001 m 84.5 240.60001 l 84.5 240.60001 m 85.60001 241 l 85.60001 241 m 86.89999 241.3 l 86.89999 241.3 m 88.2 241.39999 l 88.2 241.39999 m 88.8 241.39999 l 97.89999 239.2 m 99.10001 238.60001 l 99.10001 238.60001 m 100.7 237.7 l 100.7 237.7 m 102.3 236.7 l 102.3 236.7 m 103.8 235.60001 l 103.8 235.60001 m 106.60001 233.2 l 106.60001 233.2 m 107.8 231.89999 l 107.8 231.89999 m 109 230.5 l 109 230.5 m 110 229.10001 l 110 229.10001 m 110.89999 227.7 l S 110.89999 227.7 m 111.7 226.3 l 111.7 226.3 m 112.3 224.89999 l 112.3 224.89999 m 112.8 223.5 l 112.8 223.5 m 113.10001 222.10001 l 113.10001 222.10001 m 113.3 220.8 l 113.3 220.8 m 113.3 219.5 l 113.3 219.5 m 113.2 218.3 l 113.2 218.3 m 112.89999 217.2 l 112.89999 217.2 m 112.39999 216.2 l 112.39999 216.2 m 111.8 215.3 l 111.8 215.3 m 111.10001 214.5 l 111.10001 214.5 m 110.2 213.89999 l 110.2 213.89999 m 109.2 213.3 l 109.2 213.3 m 108 212.89999 l 108 212.89999 m 106.8 212.60001 l 106.8 212.60001 m 105.39999 212.5 l 105.39999 212.5 m 104 212.5 l 104 212.5 m 102.5 212.60001 l 102.5 212.60001 m 101 212.89999 l 101 212.89999 m 99.39999 213.3 l 99.39999 213.3 m 97.8 213.8 l 97.8 213.8 m 96.2 214.5 l 96.2 214.5 m 94.5 215.3 l 94.5 215.3 m 93 216.2 l 93 216.2 m 92.39999 216.60001 l 353.8 283 m 354 283.89999 l 354 283.89999 m 354 285.7 l 354 285.7 m 353.8 286.60001 l 353.8 286.60001 m 353.5 287.5 l 353.5 287.5 m 352.5 289.10001 l 352.5 289.10001 m 351.89999 289.89999 l 351.89999 289.89999 m 351.10001 290.60001 l 351.10001 290.60001 m 350.3 291.2 l 350.3 291.2 m 349.3 291.8 l 349.3 291.8 m 348.3 292.3 l 348.3 292.3 m 347.3 292.7 l 347.3 292.7 m 344.89999 293.3 l 344.89999 293.3 m 343.7 293.39999 l 343.7 293.39999 m 342.5 293.5 l 342.5 293.5 m 341.2 293.5 l 341.2 293.5 m 340 293.3 l 340 293.3 m 338.8 293.10001 l 338.8 293.10001 m 338.39999 293 l 333.60001 291.10001 m 333.2 290.89999 l 333.2 290.89999 m 331.39999 289.5 l 331.39999 289.5 m 330.7 288.7 l 330.7 288.7 m 330.10001 287.89999 l 330.10001 287.89999 m 329.5 287 l 329.5 287 m 329.10001 286.10001 l 329.10001 286.10001 m 328.8 285.2 l 336.10001 291.89999 m 341.3 284.10001 l 351.7 290 m 340.39999 285.5 l 339.5 286.8 m 350.3 291.2 l S 348.5 292.2 m 338.60001 288.2 l 337.7 289.5 m 346.2 293 l 343.10001 293.5 m 336.8 290.89999 l 330.2 275.5 m 330.60001 275 l 330.60001 275 m 331.10001 274.5 l 331.10001 274.5 m 331.7 274.2 l 331.7 274.2 m 332.39999 274 l 332.39999 274 m 333.2 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CS ChemDraw DrawingChemDraw Interchange FormatChemDraw.Document.4.59q Oh+'0  0 < H T`hpx ss John Wood ohnohnNormalo John Wood       !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~      !"#$%&'()*+,-./0123456789:;<=>?@ABEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}~VjCD0100ChemDraw 4.5KMicrosoft Word - C:\Yew W6 Folders\Wayne\organic letters\Ingenol data.docko2  B7 $$$$xf  `  xg'dd'`Arial 27fmfffmt  3   c  \u&WordMicrosoft Word  Courier New- @Times New Roman-&.  - "-   &&-  !-uC (L@ @ @@@@@`@```@@@@ @ @ @ @@ @ @ ` @` ` ` @ @ @ @ @@@@@ @@ @ @ @@@@@@@@@@`@@`@`@`@@@@@@@@@@@@@@@@@@@@@`@``` `@ ` ` `@`@@`@`@```@```````@````@````@````@```@ @ @@@@@`@```@@@@@ @ @@@@@`@```@@@@@ @ @@@@@`@```@@@@@ @ @@@@@`@```@@@@&&&%%MSEPS Preamble [Softek v3.6] /pp_save save def /showpage {} def /s_rebeko 66 dict def s_rebeko begin /pict_box_x1 63 def /pict_box_y1 108 def /pict_box_x2 466 def /pict_box_y2 579 def /scale_the_picture false def /pp_clip false def /CB { { /pp_cy exch def /pp_cx exch def /pp_cht exch def /pp_cwd exch def } stopped not { /pp_clip true def } if } def /B { { /pict_y1 exch def /pict_x1 exch def /pict_y2 exch def /pict_x2 exch def } stopped not { /scale_the_picture true def } if } def - "-  &%pp_clip { pp_cx pp_cy moveto pp_cwd 0 rlineto 0 pp_cht rlineto pp_cwd neg 0 rlineto clip newpath } if scale_the_picture { /pict_y2 pict_y2 pict_y1 add def /pict_x2 pict_x2 pict_x1 add def /scale_x pict_x2 pict_x1 sub pict_box_x2 pict_box_x1 sub div def /scale_y pict_y2 pict_y1 sub pict_box_y1 pict_box_y2 sub div def /pict_kx pict_x1 scale_x pict_box_x1 mul sub def /pict_ky pict_y1 scale_y pict_box_y2 mul sub def pict_kx pict_ky translate scale_x scale_y scale } if end &%%!PS-Adobe-3.0 EPSF-3.0 %%Title: (ortep.pdf) %%Version: 1 2 %%CreationDate: (D:20010312184723) %%DocumentData: Clean7Bit %%BoundingBox: 63 108 466 579 %%Pages: 0 %%DocumentProcessColors: Black %%DocumentSuppliedResources: %%+ procset (Adobe Acrobat - PDF operators) 1.2 0 %%EndComments 63 108 moveto 466 108 lineto 466 579 lineto 63 579 lineto closepath clip newpath %%BeginProlog %%EndProlog %%BeginSetup /currentpacking where{pop currentpacking true setpacking}if %%BeginResource: procset pdfvars %%Copyright: Copyright 1987-1999 Adobe Systems Incorporated. All Rights Reserved. %%Version: 4.0 1 %%Title: definition of dictionary of variables used by PDF & PDFText procsets userdict /PDF 150 dict put userdict /PDFVars 86 dict dup begin put /_save 0 def /_cshow 0 def /InitAll 0 def /TermAll 0 def /DocInitAll 0 def /DocTermAll 0 def /_lp /none def /_doClip 0 def /sfc 0 def /_sfcs 0 def /_sfc 0 def /ssc 0 def /_sscs 0 def /_ssc 0 def /_fcs 0 def /_scs 0 def /_fp 0 def /_sp 0 def /AGM_MAX_CS_COMPONENTS 10 def /_fillColors [ 0 1 AGM_MAX_CS_COMPONENTS { array } for ] def /_strokeColors [ 0 1 AGM_MAX_CS_COMPONENTS { array } for ] def /_fc null def /_sc null def /DefaultGray [/DeviceGray] def /DefaultRGB [/DeviceRGB] def /DefaultCMYK [/DeviceCMYK] def /_inT false def /_tr -1 def /_rise 0 def /_ax 0 def /_cx 0 def /_ld 0 def /_tm matrix def /_ctm matrix def /_mtx matrix def /_hy (-) def /_fScl 0 def /_hs 1 def /_pdfEncodings 2 array def /_baselineadj 0 def /_fTzero false def /_Tj 0 def /_italMtx [1 0 .212557 1 0 0] def /_italMtx_WMode1 [1 -.212557 0 1 0 0] def /_italMtxType0 [1 0 .1062785 1 0 0] def /_italMtx_WMode1Type0 [1 -.1062785 0 1 0 0] def /_basefont 0 def /_basefonto 0 def /_pdf_oldCIDInit null def /_pdf_FontDirectory 30 dict def /_categories 10 dict def /_sa? true def /_op? false def /_OP? false def /_opmode 0 def /_ColorSep5044? false def /_tmpcolr? [] def /_tmpop? {} def /_processColors 0 def /_defaulttransfer currenttransfer def /_defaultflatness currentflat def /_defaulthalftone null def /_defaultcolortransfer null def /_defaultblackgeneration null def /_defaultundercolorremoval null def /_defaultcolortransfer null def end %%EndResource PDFVars begin PDF begin %%BeginResource: procset pdfutil %%Copyright: Copyright 1993-1999 Adobe Systems Incorporated. All Rights Reserved. %%Version: 4.0 1 %%Title: Basic utilities used by other PDF procsets /bd {bind def} bind def /ld {load def} bd /dd { PDFVars 3 1 roll put } bd /xdd { exch dd } bd /Level2? systemdict /languagelevel known { systemdict /languagelevel get 2 ge } { false } ifelse def /Level3? systemdict /languagelevel known {systemdict /languagelevel get 3 eq } { false } ifelse def /getifknown { 2 copy known { get true } { pop pop false } ifelse } bd /here { currentdict exch getifknown } bd /isdefined? { where { pop true } { false } ifelse } bd /StartLoad { dup dup not { /_save save dd } if } bd /EndLoad { if not { _save restore } if } bd %%EndResource %%BeginResource: l2compat %%Copyright: Copyright 1987-1993 Adobe Systems Incorporated. All Rights Reserved. /cshow isdefined? not StartLoad { /cshow { exch /_cshow xdd { 0 0 _cshow exec } forall } bd } EndLoad /setcmykcolor isdefined? not StartLoad { /setcmykcolor { 1 sub 4 1 roll 3 { 3 index add neg dup 0 lt { pop 0 } if 3 1 roll } repeat setrgbcolor pop } bd } EndLoad /rectclip isdefined? not StartLoad { /re 0 def /rectclip { newpath re clip newpath } bd } EndLoad /execform isdefined? not StartLoad { /execform { gsave dup begin Matrix concat BBox aload pop exch 3 index sub exch 2 index sub rectclip PaintProc end grestore } def } EndLoad /sethalftone isdefined? not StartLoad { /sethalftone { begin HalftoneType 1 eq { Frequency Angle /SpotFunction load setscreen } if end } bd } EndLoad %%EndResource %%BeginResource: procset pdf %%Version: 4.0 1 %%Copyright: Copyright 1998-1999 Adobe Systems Incorporated. All Rights Reserved. %%Ti&%tle: General operators for PDF, common to all Language Levels. [/b/B/b*/B*/BDC/BI/BMC/BT/BX/c/cm/cs/CS/d/d0/d1/Do/DP/EI/EMC/ET/EX/f/f*/g/G/gs /h/i/j/J/k/K/l/m/M/MP/n/q/Q/re/rg/RG/ri/s/S/sc/SC/scn/SCN/sg/Tc/Td/TD/Tf/Tj/TJ /TL/Tm/Tr/Ts/Tw/Tz/T*/v/w/W/W*/y/'/" /applyInterpFunc/applystitchFunc/domainClip/EF/encodeInput/gsDI/ilp/icl /initgs/int/limit/PS/rangeClip/RC/rf/makePat ] {null def} bind forall /v { currentpoint 6 2 roll c } bd /y { 2 copy c } bd /h/closepath ld /d/setdash ld /j/setlinejoin ld /J/setlinecap ld /M/setmiterlimit ld /w/setlinewidth ld /i { dup 0 eq { pop _defaultflatness } if setflat } bd /gsDI { begin /Font here { aload pop Tf } if /LW here { w } if /LC here { J } if /LJ here { j } if /ML here { M } if /D here { aload pop d } if end } bd /ilp { /_lp /none dd } bd /sfc { _lp /fill ne { _sfcs _sfc /_lp /fill dd } if } dd /ssc { _lp /stroke ne { _sscs _ssc /_lp /stroke dd } if } dd /icl { /_doClip 0 dd } bd /W { /_doClip 1 dd } bd /W* { /_doClip 2 dd } bd /n { {{} {clip} {eoclip}} _doClip get exec icl newpath } bd /s { h S } bd /B { q f Q S } bd /B* { q f* Q S } bd /b { h B } bd /b* { h B* } bd /q/save ld /Q { restore ilp } bd /GetCSFamily { dup type /arraytype eq {0 get} if } bd /GetCompsDict 11 dict begin /DeviceGray { pop 1 } bd /DeviceRGB { pop 3 } bd /DeviceCMYK { pop 4 } bd /CIEBasedA { pop 1 } bd /CIEBasedABC { pop 3 } bd /CIEBasedDEF { pop 3 } bd /CIEBasedDEFG { pop 4 } bd /DeviceN { 1 get length } bd /Separation { pop 1 } bd /Indexed { pop 1 } bd /Pattern { pop 0 } bd currentdict end def /GetComps { GetCompsDict 1 index GetCSFamily get exec } bd /cs { dup _fcs eq { pop } { dup /_fcs xdd GetComps _fillColors exch get /_fc xdd /_fp null dd } ifelse } bd /CS { dup _scs eq { pop } { dup /_scs xdd GetComps _strokeColors exch get /_sc xdd /_sp null dd } ifelse } bd /sc { _fc astore pop ilp } bd /SC { _sc astore pop ilp } bd /g { DefaultGray cs sc } bd /rg { DefaultRGB cs sc } bd /k { DefaultCMYK cs sc } bd /G { DefaultGray CS SC } bd /RG { DefaultRGB CS SC } bd /K { DefaultCMYK CS SC } bd /cm { _mtx astore concat } bd /re { 4 2 roll m 1 index 0 rlineto 0 exch rlineto neg 0 rlineto h } bd /RC/rectclip ld /EF/execform ld /PS { cvx exec } bd /initgs { /DefaultGray [/DeviceGray] dd /DefaultRGB [/DeviceRGB] dd /DefaultCMYK [/DeviceCMYK] dd 0 g 0 G [] 0 d 0 j 0 J 10 M 1 w true setSA /_op? false dd /_OP? false dd /_opmode 0 dd /_defaulttransfer load 5 dict begin settransfer end 0 i newpath } bd /int { dup 2 index sub 3 index 5 index sub div 6 -2 roll sub mul exch pop add exch pop } bd /limit { dup 2 index le { exch } if pop dup 2 index ge { exch } if pop } bd /domainClip { Domain aload pop 3 2 roll limit } bd /applyInterpFunc { 0 1 DimOut 1 sub { dup C0 exch get exch dup C1 exch get exch 3 1 roll 1 index sub 3 index N exp mul add exch currentdict /Range_lo known { dup Range_lo exch get exch Range_hi exch get 3 2 roll limit } { pop } ifelse exch } for pop } bd /encodeInput { NumParts 1 sub 0 1 2 index { dup Bounds exch get 2 index gt { exit } { dup 3 index eq { exit } { pop } ifelse } ifelse } for 3 2 roll pop dup Bounds exch get exch dup 1 add Bounds exch get exch 2 mul dup Encode exch get exch 1 add Encode exch get int } bd /rangeClip { exch dup Range_lo exch get exch Range_hi exch get 3 2 roll limit } bd /applyStitchFunc { Functions exch get exec currentdict /Range_lo known { 0 1 DimOut 1 sub { DimOut 1 add -1 roll rangeClip } for } if } bind def %%EndResource %%BeginResource: procset sep_ops %%Version: 4.0 1 %%Copyright: Copyright 1987-1999 Adobe Systems Incorporated. All Rights Reserved. %%Title: Support for Separations in Level 1, following the conventions of Tech Note 5044 userdict /sep_ops 50 dict dup begin put /bdef {bind def} bind def /xdef {exch def} bdef /colorimagebuffer { 0 1 2 index length 1 sub { dup 2 index exch get 255 exch sub 2 index 3 1 r&%oll put } for } bdef /addprocs { [ 3 1 roll /exec load dup 3 1 roll ] cvx } bdef /L1? { systemdict /languagelevel known { systemdict /languagelevel get 2 lt }{ true } ifelse } bdef /colorexists { statusdict /processcolors known { statusdict /processcolors get exec }{ /deviceinfo where { pop deviceinfo /Colors known { deviceinfo /Colors get statusdict /processcolors { deviceinfo /Colors known { deviceinfo /Colors get }{ 1 } ifelse } put }{ 1 } ifelse }{ 1 } ifelse } ifelse 1 gt } bdef /colorplate colorexists { 0 } { 5 } ifelse def /negativecolorplate false def /setcmykcolor where { pop gsave 1 0 0 0 setcmykcolor systemdict /currentgray get exec 1 exch sub 0 1 0 0 setcmykcolor systemdict /currentgray get exec 1 exch sub 0 0 1 0 setcmykcolor systemdict /currentgray get exec 1 exch sub 0 0 0 1 setcmykcolor systemdict /currentgray get exec 1 exch sub 4 {4 copy} repeat grestore 1 dict begin /foureq { 4 index eq 8 1 roll 4 index eq 8 1 roll 4 index eq 8 1 roll 4 index eq 8 1 roll pop pop pop pop and and and } def 1 0 0 0 foureq {/colorplate 1 store} if 0 1 0 0 foureq {/colorplate 2 store} if 0 0 1 0 foureq {/colorplate 3 store} if 0 0 0 1 foureq {/colorplate 4 store} if 0 0 0 0 foureq {/colorplate 6 store} if end } if 0 systemdict /currenttransfer get exec exec 1 systemdict /currenttransfer get exec exec 2 copy eq { /colorplate 6 store pop /negativecolorplate exch 0.5 lt store } { gt /negativecolorplate exch store } ifelse /findcmykcustomcolor where { pop } { /findcmykcustomcolor { [ 6 1 roll ] readonly } bdef } ifelse /setoverprint where { pop }{ /setoverprint { pop } bdef } ifelse /setcustomcolor where { pop }{ L1? { /setcustomcolor { exch aload pop pop 4 { 4 index mul 4 1 roll } repeat 5 -1 roll pop setcmykcolor } bdef }{ /setcustomcolor { exch [ exch /Separation exch dup 4 get exch /DeviceCMYK exch 0 4 getinterval [ exch /dup load exch cvx {mul exch dup} /forall load /pop load dup] cvx ] setcolorspace setcolor } bdef } ifelse } ifelse /ik 0 def /iy 0 def /im 0 def /ic 0 def /imagetint { ic .3 mul im .59 mul iy .11 mul ik add add add dup 1 gt {pop 1} if } bdef /setcmykcolor where { pop }{ /setcmykcolor { /ik xdef /iy xdef /im xdef /ic xdef imagetint 1 exch sub setgray } bdef } ifelse /customcolorimage where { pop }{ L1? { /customcolorimage{ gsave colorexists { aload pop pop /ik xdef /iy xdef /im xdef /ic xdef currentcolortransfer {ik mul ik sub 1 add} addprocs 4 1 roll {iy mul iy sub 1 add} addprocs 4 1 roll {im mul im sub 1 add} addprocs 4 1 roll {ic mul ic sub 1 add} addprocs 4 1 roll setcolortransfer /magentabuf 0 string def /yellowbuf 0 string def /blackbuf 0 string def { colorimagebuffer dup length magentabuf length ne { dup length dup dup /magentabuf exch string def /yellowbuf exch string def /blackbuf exch string def } if dup magentabuf copy yellowbuf copy blackbuf copy pop } addprocs {magentabuf}{yellowbuf}{blackbuf} true 4 colorimage }{ aload pop pop /ik xdef /iy xdef /im xdef /ic xdef /tint imagetint def currenttransfer {tint mul 1 tint sub add} addprocs settransfer image } ifelse grestore } bdef }{ /customcolorimage { gsave [ exch /Separation exch dup 4 get exch /DeviceCMYK exch 0 4 getinterval [ exch /dup load exch cvx {mul exch dup} /forall load /pop load dup] cvx ] setcolorspace 10 dict begin /ImageType 1 def /DataSource exch def /ImageMatrix exch def /BitsPerComponent exch def /Height exch def /Width exch def /Decode [1 0] def currentdict end image grestore } bdef } ifelse } ifelse /setseparationgray where { pop }{ L1? { /setseparationgray { 1 exch sub dup dup dup setcmykcolor } bdef }{ /setseparationgray { [/Separation /All /DeviceCMYK {dup dup dup}] setcolorspace 1 exch sub setcolor } bdef } ifelse } ifelse /separationimage where { pop } { /separationimage { gsave 1 1 1 1 (All) findcmykcustomcolor customcolorimage grestore } bdef } ifelse currentdict readonly pop end&% %%EndResource %%BeginResource: procset pdflev15044 %%Version: 4.0 1 %%Copyright: Copyright 1987-1990 Adobe Systems Incorporated. All Rights Reserved. %%LanguageLevel: 1 %%Title: PDF operators, Level 1, with emulated separations (TN 5044) /_ColorSep5044? true dd currentscreen dup type /dicttype eq { /_defaulthalftone xdd pop pop } { 5 dict begin 1 [/HalftoneType /SpotFunction /Angle /Frequency ] { exch def } forall /_defaulthalftone currentdict end dd } ifelse /currentcolortransfer where { pop /_defaultcolortransfer [ currentcolortransfer ] dd } { /setcolortransfer { settransfer pop pop pop } bd /_defaultcolortransfer [currenttransfer dup dup dup] dd } ifelse /initialize { sep_ops begin 50 dict begin _defaulthalftone sethalftone } bd /terminate { end end } bd /pl { transform 0.25 sub round 0.25 add exch 0.25 sub round 0.25 add exch itransform } bd /m { _sa? { pl } if moveto } bd /l { _sa? { pl } if lineto } bd /c { _sa? { pl } if curveto } bd /setSA { /_sa? xdd } bd /AlmostFull? { dup maxlength exch length sub 2 le } bd /Expand { 1 index maxlength mul cvi dict dup begin exch { def } forall end } bd /xput { 3 2 roll dup 3 index known not { dup AlmostFull? { 1.5 Expand } if } if dup 4 2 roll put } bd /defineRes { _categories 1 index known not { /_categories _categories 2 index 10 dict xput store } if _categories exch 2 copy get 5 -1 roll 4 index xput put } bd /findRes { _categories exch get exch get } bd /ri/pop ld /L1setcolor { aload length dup 0 eq { pop .5 setgray } { dup 1 eq { pop setgray } { 3 eq { setrgbcolor } { setcmykcolor } ifelse } ifelse } ifelse } bind dd /_sfcs { } dd /_sscs { } dd /scn { sc } bd /SCN { SC } bd /rf {re f} bd /concattransferfuncs { [ 3 1 roll /exec load exch /exec load ] cvx } bd /concatandsettransfer { /_defaulttransfer load concattransferfuncs settransfer } bd /concatandsetcolortransfer { colorplate 0 eq { _defaultcolortransfer aload pop 8 -1 roll 5 -1 roll concattransferfuncs 7 1 roll 6 -1 roll 4 -1 roll concattransferfuncs 5 1 roll 4 -1 roll 3 -1 roll concattransferfuncs 3 1 roll concattransferfuncs setcolortransfer } if colorplate 1 ge colorplate 4 le and { 4 colorplate sub index 4 { exch pop } repeat concatandsettransfer } if colorplate 5 ge { 0 index 4 { exch pop } repeat concatandsettransfer } if } bd /tn5044sethalftone { begin HalftoneType 5 eq { [/Default /Cyan /Magenta /Yellow /Black /Default /Default /Default] colorplate get here not { /Default here not { currentdict } if } if } { currentdict } ifelse end begin /TransferFunction here { concatandsettransfer currentdict dup length dict begin { 1 index /TransferFunction ne { def } { pop pop } ifelse } forall currentdict end } { currentdict } ifelse end sethalftone } bd /gs { begin /SA here { /_sa? xdd } if /OP here { /_OP? xdd } if /op here { /_op? xdd } { /OP here { /_op? xdd } if } ifelse /TR here { dup xcheck { concatandsettransfer } { aload pop concatandsetcolortransfer } ifelse } if /HT here { tn5044sethalftone } if /FL here { i } if currentdict gsDI end } bd /_sfc { _fp null eq { _fcs type /arraytype eq {_fcs 0 get /Separation eq { _fcs 1 get /All eq { _fc aload pop 1 exch sub /setseparationgray where pop begin setseparationgray end } { 1 _fcs 3 get exec _fcs 1 get /findcmykcustomcolor where pop begin findcmykcustomcolor end _fc aload pop /setcustomcolor where pop begin setcustomcolor end } ifelse } { _fc L1setcolor } ifelse } { _fc L1setcolor } ifelse } { _fc L1setcolor } ifelse _op? setoverprint } bind dd /_ssc { _sp null eq { _scs type /arraytype eq {_scs 0 get /Separation eq { _scs 1 get /All eq { _sc aload pop 1 exch sub /setseparationgray where pop begin setseparationgray end } { 1 _scs 3 get exec _scs 1 get /findcmykcustomcolor where pop begin findcmykcustomcolor end _sc aload pop /setcustomcolor where pop begin setcustomcolor end } ifelse } { _sc L1setcolor } ifelse } { _sc&% L1setcolor } ifelse } { _sc L1setcolor } ifelse _OP? setoverprint } bind dd /f { { { sfc fill } {gsave sfc fill grestore clip newpath icl ilp} {gsave sfc fill grestore eoclip newpath icl ilp} } _doClip get exec } bd /f* { { { sfc eofill } {gsave sfc eofill grestore clip newpath icl ilp} {gsave sfc eofill grestore eoclip newpath icl ilp} } _doClip get exec } bd /S { { { ssc stroke } {gsave ssc stroke grestore clip newpath icl ilp} {gsave ssc stroke grestore eoclip newpath icl ilp} } _doClip get exec } bd /rf {re f} bd %%EndResource currentdict readonly pop end end /currentpacking where {pop setpacking}if PDFVars/DocInitAll{[]{/docinitialize get exec}forall }put PDFVars/InitAll{[PDF]{/initialize get exec}forall initgs}put PDFVars/TermAll{[PDF]{/terminate get exec}forall}put PDFVars begin PDF begin PDFVars/DocInitAll get exec PDFVars/InitAll get exec PDFVars/TermAll get exec end end %%EndSetup PDFVars begin PDF begin PDFVars/InitAll get exec 63 108 403 471 re W n /N23 16 dict dup begin /SA false def /TR {}def /SM 0.02 def end /ExtGState defineRes pop 0 G 0 J 0 j 0.39999 w 10 M []0 d /N23 /ExtGState findRes gs 1 i 182.8 132 m 182.2 131.5 l 182.2 131.5 m 181.8 131 l 181.8 131 m 181.2 129.8 l 181.2 129.8 m 181.10001 129.10001 l 181.10001 129.10001 m 181.10001 128.3 l 181.10001 128.3 m 181.3 127.60001 l 181.3 127.60001 m 181.5 126.8 l 181.5 126.8 m 181.89999 126 l 181.89999 126 m 182.39999 125.3 l 182.39999 125.3 m 183.60001 123.7 l 183.60001 123.7 m 184.39999 122.89999 l 184.39999 122.89999 m 186.2 121.5 l 186.2 121.5 m 187.3 120.89999 l 187.3 120.89999 m 188.3 120.2 l 188.3 120.2 m 190.7 119.2 l 190.7 119.2 m 191.8 118.7 l 191.8 118.7 m 193.10001 118.3 l 193.10001 118.3 m 194.3 118 l 194.3 118 m 196.7 117.60001 l 196.7 117.60001 m 197.8 117.5 l 197.8 117.5 m 199 117.5 l 199 117.5 m 200 117.60001 l 200 117.60001 m 201 117.7 l 201 117.7 m 202 117.89999 l 202 117.89999 m 202.8 118.2 l 202.8 118.2 m 203.60001 118.60001 l 203.60001 118.60001 m 204.2 119 l 191.60001 118.8 m 193.5 125.5 l 181.10001 128.7 m 193.2 124.39999 l 192.89999 123.3 m 181.3 127.39999 l 181.89999 125.89999 m 192.60001 122.2 l 192.2 121 m 183.10001 124.3 l 185.10001 122.3 m 191.89999 119.89999 l 207.10001 122.89999 m 207.2 123.5 l 207.2 123.5 m 207.2 124.10001 l 207.2 124.10001 m 207 124.7 l 207 124.7 m 206.7 125.3 l 206.7 125.3 m 206.3 125.89999 l 206.3 125.89999 m 205.10001 127.10001 l 205.10001 127.10001 m 204.3 127.7 l 204.3 127.7 m 203.39999 128.3 l 203.39999 128.3 m 201.39999 129.3 l 201.39999 129.3 m 200.2 129.8 l 200.2 129.8 m 197.8 130.60001 l 197.8 130.60001 m 195.2 131.2 l 195.2 131.2 m 193.8 131.5 l 193.8 131.5 m 192.5 131.60001 l 192.5 131.60001 m 191.2 131.7 l 191.2 131.7 m 189.89999 131.8 l 189.89999 131.8 m 188.60001 131.8 l 188.60001 131.8 m 187.39999 131.7 l 187.39999 131.7 m 186.2 131.60001 l 186.2 131.60001 m 185.10001 131.39999 l 185.10001 131.39999 m 184.10001 131.2 l 184.10001 131.2 m 183.2 130.89999 l 183.2 130.89999 m 182.3 130.5 l 182.3 130.5 m 181.60001 130.10001 l 181.60001 130.10001 m 181 129.7 l 181 129.7 m 180.5 129.2 l 180.5 129.2 m 180.2 128.7 l 180.2 128.7 m 180 128.10001 l 181.3 129.89999 m 193.5 125.5 l 197.5 130.7 m 191.5 126.2 l 189.39999 127 m 195.2 131.2 l S 192.60001 131.60001 m 187.39999 127.7 l 185.39999 128.39999 m 189.89999 131.8 l 186.7 131.7 m 183.3 129.2 l 188 117.5 m 188.39999 117.39999 l 188.39999 117.39999 m 188.8 117.39999 l 188.8 117.39999 m 189.2 117.5 l 189.2 117.5 m 190.2 117.89999 l 190.2 117.89999 m 190.7 118.2 l 190.7 118.2 m 191.3 118.60001 l 191.3 118.60001 m 193.10001 120.10001 l 193.10001 120.10001 m 193.8 120.7 l 193.8 120.7 m 195.60001 122.8 l 195.60001 122.8 m 196.2 123.60001 l 196.2 123.60001 m 196.7 124.39999 l 196.7 124.39999 m 197.3 125.2 l 197.3 125.2 m 197.8 126 l 197.8 126 m 198.2 126.8 l 198.2 126.8 m 198.60001 127.5 l 198.60001 127.5 m 19&%8.89999 128.3 l 198.89999 128.3 m 199.5 129.7 l 199.5 129.7 m 199.7 130.39999 l 199.7 130.39999 m 199.8 131 l 199.8 131 m 199.89999 131.5 l 199.89999 131.5 m 199.89999 132 l 199.89999 132 m 199.8 132.5 l 199.8 132.5 m 199.7 132.8 l 199.7 132.8 m 199.5 133.2 l 199.5 133.2 m 199.3 133.39999 l 199.3 133.39999 m 199 133.5 l 199.60001 130 m 193.5 125.5 l 192.60001 119.7 m 194.5 126.3 l 195.60001 127 m 193.7 120.7 l 194.89999 122 m 196.60001 127.8 l 197.60001 128.5 m 196.10001 123.5 l 197.5 125.60001 m 198.60001 129.3 l 182.8 132 m 183.7 132.60001 l 183.7 132.60001 m 184.7 133.2 l 184.7 133.2 m 185.8 133.60001 l 185.8 133.60001 m 187 134 l 187 134 m 188.2 134.3 l 188.2 134.3 m 190.8 134.7 l 190.8 134.7 m 193 134.7 l 196.2 134.3 m 197.5 134 l 197.5 134 m 198.8 133.60001 l 198.8 133.60001 m 200 133.2 l 200 133.2 m 201.2 132.60001 l 201.2 132.60001 m 202.2 132 l 202.2 132 m 203.3 131.3 l 203.3 131.3 m 204.2 130.60001 l 204.2 130.60001 m 205 129.8 l 205 129.8 m 205.7 129 l 205.7 129 m 206.3 128.2 l 206.3 128.2 m 207.10001 126.39999 l 207.10001 126.39999 m 207.3 125.5 l 207.3 125.5 m 207.3 123.7 l 207.3 123.7 m 207.10001 122.8 l 207.10001 122.8 m 206.8 122 l 206.8 122 m 206.3 121.2 l 206.3 121.2 m 205.7 120.39999 l 205.7 120.39999 m 205.10001 119.7 l 205.10001 119.7 m 204.2 119 l 204.2 119 m 203.3 118.39999 l 203.3 118.39999 m 201.3 117.39999 l 201.3 117.39999 m 200.10001 117 l S 200.10001 117 m 198.89999 116.7 l 198.89999 116.7 m 197.60001 116.5 l 197.60001 116.5 m 196.3 116.39999 l 196.3 116.39999 m 194.89999 116.3 l 194.89999 116.3 m 193.60001 116.39999 l 193.60001 116.39999 m 192.2 116.5 l 192.2 116.5 m 190.89999 116.7 l 190.89999 116.7 m 189.60001 117 l 189.60001 117 m 188.3 117.39999 l 188.3 117.39999 m 185.89999 118.39999 l 185.89999 118.39999 m 184.8 119 l 184.8 119 m 183.8 119.7 l 183.8 119.7 m 182.89999 120.39999 l 182.89999 120.39999 m 182.10001 121.2 l 182.10001 121.2 m 181.39999 122 l 181.39999 122 m 180.8 122.89999 l 180.8 122.89999 m 180.3 123.7 l 180.3 123.7 m 180 124.60001 l 180 124.60001 m 179.8 125.5 l 179.8 125.5 m 179.7 126.39999 l 179.7 126.39999 m 179.8 127.3 l 179.8 127.3 m 180 128.2 l 180 128.2 m 180.3 129.10001 l 180.3 129.10001 m 180.7 129.89999 l 180.7 129.89999 m 181.3 130.60001 l 181.3 130.60001 m 182 131.39999 l 182 131.39999 m 182.8 132 l 398 242.10001 m 398.3 242 l 398.3 242 m 398.7 241.39999 l 398.7 241.39999 m 399.10001 240.60001 l 399.10001 240.60001 m 399.5 239.39999 l 399.5 239.39999 m 399.89999 237.89999 l 399.89999 237.89999 m 400.3 236.2 l 400.3 236.2 m 400.89999 232.39999 l 400.89999 232.39999 m 401.10001 230.39999 l 401.10001 230.39999 m 401.3 228.5 l 401.3 228.5 m 401.39999 226.7 l 401.39999 226.7 m 401.39999 225.2 l 401.39999 225.2 m 401.3 223.89999 l 401.3 223.89999 m 401.10001 222.89999 l 401.10001 222.89999 m 400.89999 222.3 l 400.89999 222.3 m 400.60001 222.10001 l 401.2 229.3 m 399.3 232.10001 l 398.8 241.10001 m 399.60001 231.60001 l 399.89999 231.2 m 399.2 240.3 l 399.60001 239.10001 m 400.3 230.7 l 400.60001 230.3 m 400 237.39999 l 400.5 235.10001 m 400.89999 229.8 l 387.2 226.60001 m 386.3 228.2 l 386.3 228.2 m 385.89999 230.10001 l S 385.89999 230.10001 m 386 232 l 386 232 m 386.60001 233.89999 l 386.60001 233.89999 m 387.8 235.8 l 387.8 235.8 m 389.3 237.5 l 389.3 237.5 m 391.3 239 l 391.3 239 m 393.5 240.2 l 393.5 240.2 m 396 241.2 l 396 241.2 m 398.60001 241.7 l 398.60001 241.7 m 401.2 242 l 401.2 242 m 403.8 241.8 l 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