ࡱ> [ bjbj ojjtmlbbb( BBBV>>>>4VI****dEEEEEEE@J `L$EBE^E9*dDI999"l*:BdE9E99+BaD,BDd V >99yDDZI0IDM99^MD9VVSupporting Information Synthesis of Stereotriads by Oxymercuration of Substituted Cyclopropylcarbinols Janine Cossy,* Nicolas Blanchard and Christophe Meyer General Procedures: All reactions were performed using oven-dried glassware under an atmosphere of argon. Dry ether and THF were obtained by distillation from sodium-benzophenone, and dichloromethane from CaH2. Other reagents were obtained from commercial sources and used as received. Purification by flash chromatography was performed using SDS silica gel 60 (0.04-0.06 mm). NMR spectra were recorded on a Bruker AC 300, at 300MHz and 75 MHz for 1H and 13C respectively. IR spectra were recorded on a Perkin Elmer 298. Mass spectra were obtained by GC-MS, with electron impact ionization at 70 eV, using a Hewlett Packard HP 5971. Elemental analyses were performed by the Centre Rgional de Microanalyses de lUniversit Paris VI. HRMS were performed by the Laboratoire de Spectrochimie de lEcole Normale Suprieure Ulm. Preparation of cyclopropylcarbinols 2a, 2b and 2c. (2R*)-2-[(1S*,2S*)-2-(Hydroxymethyl)cyclopropyl]propyl 2,2-dimethylpropanoate 2a. To a solution of 1a, (500 mg, 1.36 mmol), triethylamine (265 mL, 1.90 mmol) and DMAP (33 mg, 0.27 mol) in ether (10 mL), was added pivaloyl chloride (236 mL, 1.90 mmol). After 12 h at rt, the reaction was quenched by addition of an aqueous saturated NaHCO3 solution and extracted with ether. The combined extracts were washed with a 1M aqueous HCl solution, dried over MgSO4 and concentrated under reduced pressure to give an oil, which was dissolved in THF (5 mL). To the resulting solution at 0 C, was added tetrabutylammonium fluoride (2.0 mL, 1M in THF, 2.0 mmol), and after 3 h at rt, the reaction mixture was poured into an aqueous saturated NH4Cl solution and extracted with ether. The combined extracts were dried over MgSO4 and concentrated under reduced pressure. Purification of the crude material by flash chromatography (cyclohexane/EtOAc: 90/10 to 75/25) afforded 261 mg (90%) of 2a as a colorless oil; IR 3450, 1725, 1285, 1165, 1035 cm-1; 1H NMR d 4.09 (dd, J = 10.7 and 5.9 Hz, 1H), 3.91 (dd, J = 10.7 and 6.7 Hz, 1H), 3.49 (dd, J = 11.2 and 6.9 Hz, 1H), 3.42 (dd, J = 11.2 and 7.1 Hz, 1H), 2.31 (br s, 1H, OH), 1.20 (m, 1H), 1.20 (s, 9H), 1.02 (d, J = 6.8 Hz, 3H), 0.91 (m, 1H), 0.53-0.41 (m, 3H); 13C NMR d 178.7 (s), 68.8 (t), 66.6 (t), 38.7 (s), 37.6 (d), 27.0 (q, 3C), 21.0 (d), 20.4 (d), 16.4 (q), 8.3 (t); EI MS m/z (relative intensity) 197 (M+-OH, 2), 183 (M+-CH2OH, 2), 112 (M+-t-BuCO2H, 13), 97 (14), 95 (15), 85 (19), 81 (16), 79 (18), 69 (18), 68 (18), 57 (100), 55 (17). (2S*)-2-[(1S*,2S*)-2-(Hydroxymethyl)cyclopropyl]propyl 2,2-dimethylpropanoate 2b. This compound was prepared from 1b1,2 (500 mg, 1.36 mmol), following the procedure described for the preparation of 2a from 1a. Purification of the crude material by flash chromatography (cyclohexane/EtOAc: 90/10 to 75/25) afforded 227 mg (78%) of 2b2b as a colorless oil; IR 3400, 1720, 1290, 1165, 1030 cm-1; 1H NMR d 4.10 (dd, J= 10.7 and 5.9 Hz, 1H), 3.90 (dd, J = 10.7 and 6.7 Hz, 1H), 3.48 (dd, J = 11.2 and 6.9 Hz, 1H), 3.42 (dd, J = 11.2 and 7.1 Hz, 1H), 2.30 (br s, 1H, OH), 1.28-1.14 (m, 2H), 1.21 (s, 9H), 1.02 (d, J = 6.8 Hz, 3H), 0.53-0.41 (m, 3H); 13C NMR d 178.6 (s), 69.0 (t), 66.8 (t), 38.8 (s), 37.0 (d), 27.2 (q, 3C), 20.8 (d), 19.5 (d), 16.6 (q), 9.3 (t); EI MS m/z (relative intensity) 197 (M+-OH, 7), 183 (M+-CH2OH, 4), 112 (M+-t-BuCO2H, 14), 97 (19), 95 (19), 85 (20), 81 (15), 79 (20), 69 (16), 68 (18), 57 (100), 55 (18). (2R*)-2-[(1S*,2R*)-2-(Hydroxymethyl)cyclopropyl]propyl 2,2-dimethylpropanoate 2c. To a solution of 1c1,2 (1.28 g, 3.47 mmol) and DMAP (636 mg, 5.21 mmol) in CH2Cl2 (30mL) at 0 C, was added pivaloyl chloride (520 mL, 4.17 mmol). After 1 h at 20 C, the reaction mixture was quenched with MeOH (1 mL). After 30 min, an aqueous saturated NaHCO3 solution was added and the resulting mixture was extracted with ether. The combined extracts were dried over MgSO4, concentrated under reduced pressure, and the crude material was dissolved in THF (5 mL). To the resulting solution at 0C, was added tetrabutylammonium fluoride (7mL, 1M in THF, 7 mmol). After 3 h at rt, the reaction mixture was poured into an aqueous saturated NH4Cl solution and extracted with ether. The combined extracts were dried over MgSO4 and concentrated under reduced pressure. Purification of the crude material by flash chromatography (pentane/ether: 60/40 to 50/50) afforded 676 mg (91%) of 2c as a colorless oil; IR 3420, 1725, 1290, 1160, 1035 cm-1; 1HNMR d 4.28 (dd, J = 10.8 and 4.0 Hz, 1H), 3.78 (dd, J = 10.8 and 8.3 Hz, 1H), 3.76 (m, 1H), 3.46 (m, 1H), 2.81 (br s, 1H, OH), 1.36 (m, 1H), 1.18 (m, 1H), 1.16 (s, 9H), 1.04 (d, J = 6.7 Hz, 3H), 0.72-0.58 (m, 2H), - 0.06 (m, 1H); 13C NMR d 179.1 (s), 69.7 (t), 62.7 (t), 38.8 (s), 32.6 (d), 27.1 (q, 3C), 19.7 (d), 18.8 (d), 17.9 (q), 7.6 (t); EI MS m/z (relative intensity) 197 (M+-OH, 3), 183 (M+-CH2OH, 3), 112 (M+-t-BuCO2H, 14), 97 (17), 95 (17), 85 (21), 81 (16), 79 (20), 69 (18), 68 (16), 57 (100), 55 (16). Oxymercuration of cyclopropylcarbinols 2a, 2b and 2c. Oxymercuration of 2a: representative procedure To a solution of 2a (400 mg, 1.87 mmol) in CH2Cl2 (15 mL) was added mercuric trifluoroacetate (1.59 g, 3.74 mmol). After 1 h at 20 C with complete exclusion of light, the reaction mixture was hydrolyzed with a saturated aqueous KBr solution and extracted with CH2Cl2. The combined extracts were dried over MgSO4 and concentrated under reduced pressure. Purification of the crude material by flash chromatography (cyclohexane/EtOAc: 40/60 to 60/40) afforded 148 mg (15%) of 3a and 562 mg (60%) of 3a, as colorless oils. A third minor isomeric compound 3a (< 5%) could also be detected in the 1H NMR spectrum of the crude material prior to purification. Due to their similar polarities, this compound was occasionally found as a minor contaminant of fractions containing 3a. (1S*,2R*)-2-[(Bromomercurio)methyl]-3-hydroxy-1-((1S*)-2-hydroxy-1-methylethyl) propyl 2,2-dimethylpropanoate 3a.3a IR 3440, 1710, 1280, 1170, 1025 cm-1; 1HNMR d 4.71 (dd, J = 6.9 and 5.7 Hz, 1H), 3.61 (dd, J = 11.2 and 4.6 Hz, 2H), 3.45 (dd, J= 11.2 and 5.5 Hz, 1H), 3.38 (dd, J = 11.2 and 6.2 Hz, 1H), 2.40 (m, 1H), 1.98 (m, 1H), 1.83 (dd, J = 11.9 and 4.4 Hz, 1H), 1.73 (dd, J = 11.9 and 7.8 Hz, 1H), 1.17 (s, 9H), 0.95 (d, J = 6.9 Hz, 3H); 13C NMR d 179.6 (s), 77.8 (d), 63.2 (t), 62.4 (t), 41.3 (d), 39.1 (s), 36.5 (d), 32.5 (t), 27.2 (q, 3C), 14.6 (q). (2S*,3S*,4R*)-4-[(Bromomercurio)methyl]-3,5-dihydroxy-2-methylpentyl 2,2-dimethyl-propanoate 3 a. IR 3440, 1710, 1290, 1165, 1030 cm-1; 1H NMR d 4.29 (dd, J = 11.1 and 5.3 Hz, 1H), 4.15 (dd, J = 11.1 and 4.0 Hz, 1H), 3.96 (dd, J = 11.0 and 4.4 Hz, 1H), 3.67 (dd, J = 11.0 and 3.4 Hz, 1H), 3.31 (dd, J = 8.4 and 3.7 Hz, 1H), 2.38 (m, 1H), 2.01 (m, 1H), 2.01 (dd, J = 11.9 and 4.5 Hz, 1H), 1.88 (dd, J = 11.9 and 5.7 Hz, 1H), 1.22 (s, 9H), 1.00 (d, J = 6.8 Hz, 3H); 13C NMR d 179.6 (s), 77.3 (d), 66.5 (t), 63.6 (t), 40.1 (d), 38.9 (s), 36.8 (d), 33.7 (t), 27.2 (q, 3C), 14.3 (q). (2S*,3R*,4R*)-4-[(Bromomercurio)methyl]-3,5-dihydroxy-2-methylpentyl 2,2-dimethyl-propanoate 3  a. These spectroscopic data have been tentatively deduced from the spectra of a mixture of 3 a and 3 a. 1H NMR d 4.28 (m, 1H), 3.96 (m, 1H), 3.86 (dd, J = 10.6 and 3.7 Hz, 1H), 3.62 (m, 1H), 3.50 (m, 1H), 2.65 (m, 1H), 2.15-1.85 (m, 3H), 1.23 (s, 9H), 0.91 (d, J = 6.9 Hz, 3H); 13C NMR d 178.9 (s), 79.1 (d), 68.4 (t), 65.8 (t), 39.5 (d), 38.8 (s), 37.3 (d), 34.3 (t), 27.0 (q, 3C), 13.4 (q). Reductive demercuration of 3a and 3 a. Representative procedure: To a solution of 3a (560 mg, 1.10 mmol) containing a catalytic amount of AIBN (2 mg), in dry THF (12 mL) at rt, was added n-Bu3SnH (590mL, 2.20 mmol). Mercury began to precipitate almost instantaneously, and after 1 h at rt the reaction mixture was hydrolyzed with a 20% aqueous KF solution (3 mL). After 30 min, the reaction mixture was diluted with EtOAc, filtered through Celite, and the filtrate was extracted with EtOAc. The combined extracts were dried over MgSO4 and concentrated under reduced pressure. Purification of the crude material by flash chromatography (cyclohexane/EtOAc: 60/40 to 40/60) afforded 244 mg (96%) of 4a as a colorless oil. (1S*,2R*)-3-Hydroxy-1-((1S*)-2-hydroxy-1-methylethyl)-2-methylpropyl 2,2-dimethyl-propanoate 4a. IR 3380, 1710, 1285, 1170, 1030 cm-1; 1H NMR d 4.80 (t, J= 6.4 Hz, 1H), 3.62 (dd, J = 11.2 and 3.8 Hz, 2H), 3.44 (dd, J = 11.2 and 5.8 Hz, 2H), 3.03 (br s, 2H, OH), 2.00 (m, 2H), 1.23 (s, 9H), 1.02 (d, J = 6.9 Hz, 6H); 13C NMR d 179.4 (s), 77.4 (d), 63.2 (t, 2C), 39.0 (s), 36.5 (d, 2C), 27.1 (q, 3C), 14.4 (q, 2C); EI MS m/z (relative intensity) 173 (M+-CH3CHCH2OH, 4), 147 (5), 133 (M+-t-BuCO, 9), 103 (61), 95 (16), 89 (20), 85 (37), 82 (12), 71 (14), 69 (18), 57 (100), 55 (11). (2S*,3R*,4R*)-3,5-Dihydroxy-2,4-dimethylpentyl 2,2-dimethylpropanoate 4 a. Reductive demercuration of 3 a (150 mg, 0.29 mmol) with n-Bu3SnH (150 mL, 0.58 mmol) and a catalytic amount of AIBN in THF (4 mL) at rt, and purification by flash chromatography (cyclohexane/EtOAc: 60/40 to 40/60) afforded 66 mg (98%) of 4 a as a colorless oil; IR 3400, 1710, 1285, 1165, 1030 cm-1; 1H NMR d 4.22 (dd, J = 11.0 and 4.8 Hz, 1H), 4.13 (dd, J = 11.0 and 6.2 Hz, 1H), 3.84 (dd, J = 10.8 and 3.4 Hz, 1H), 3.61 (dd, J = 10.8 and 6.3 Hz, 1H), 3.50 (br m, 1H, OH), 3.41 (dd apparent t, J = 6.1 Hz, 1H), 3.10 (br m, 1H, OH), 2.07 (m, 1H), 1.88 (m, 1H), 1.21 (s, 9H), 1.02 (d, J = 7.0 Hz, 3H), 1.00 (d, J = 7.0 Hz, 3H); 13C NMR d 179.0 (s), 79.4 (d,), 66.8 (t), 66.0 (t), 38.9 (s), 36.5 (d), 36.0 (d), 27.2 (q, 3C), 14.7 (q), 14.5 (q). EI MS m/z (relative intensity) 173 (M+-CH3CHCH2OH,16), 103 (100), 89 (42), 85 (57), 82 (10), 71 (22), 57 (84). Oxymercuration of 2b and reductive demercuration of 3b and 3b. According to the representative procedures, oxymercuration of 2b (530 mg, 2.47 mmol) with mercuric trifluoroacetate (2.11g, 4.95 mmol) in CH2Cl2 (15 mL), subsequent reductive demercuration of the mixture of 3b and 3b with nBu3SnH (1.33 mL, 2.47 mmol) in the presence of a catalytic amount of AIBN in THF (10 mL), and purification by flash chromatography (cyclohexane/EtOAc: 70/30 to 50/50) afforded 451 mg (80%) of a regioisomeric mixture of 4b and 4b (95/5 ratio). (2R*)-3-Hydroxy-1-((1R*)-2-hydroxy-1methyl-ethyl)-2-methylpropyl 2,2-dimethyl propanoate 4b. IR 3400, 1710, 1285, 1180, 1030 cm-1; 1H NMR d 4.99 (dd, J = 9.9 and 2.2 Hz, 1H), 3.54 (dd, J = 11.2 and 3.5 Hz, 1H), 3.45 (dd, J = 11.2 and 5.5 Hz, 1H), 3.44 (dd, J = 11.1 and 4.8 Hz, 1H), 3.22 (dd, J = 11.1 and 9.4 Hz, 1H), 3.09 (br s, 1H, OH), 2.65 (br s, 1H, OH), 2.10-1.89 (m, 2H), 1.24 (s, 9H), 1.00 (d, J = 7.0 Hz, 3H), 0.85 (d, J = 7.0 Hz, 3H); 13C NMR d 179.9 (s), 73.4 (d), 64.4 (t), 64.0 (t), 39.2 (s), 36.7 (d), 36.5 (d), 27.2 (q, 3C), 13.6 (q), 9.5 (q). (2R*,3S*,4R*)-3,5-Dihydroxy-2,4-dimethylpentyl 2,2-dimethylpropanoate 4 b. IR 3400, 1730, 1710, 1290, 1170, 1030 cm-1; 1H NMR d 4.25 (dd, J = 11.0 and 8.5 Hz, 1H), 3.91 (dd, J = 11.0 and 5.5 Hz, 1H), 3.78-3.60 (m, 2H), 3.47 (d, J = 9.2 and 2.2 Hz, 1H), 2.03-1.73 (m, 2H), 1.22 (s, 9H), 0.91 (d, J = 7.0 Hz, 3H), 0.79 (d, J = 7.0 Hz, 3H); 13C NMR d 179.3 (s), 76.4 (d), 68.6 (t), 66.7 (t), 38.8 (s), 36.9 (d), 35.2 (d), 27.2 (q, 3C), 13.4 (q), 8.9 (q). Oxymercuration of cyclopropylcarbinol 2c. According to the representative procedure, oxymercuration of 2c (400 mg, 1.87 mmol) with mercuric trifluoroacetate (1.59 g, 3.74 mmol) in CH2Cl2 (15 mL), and purification by flash chromatography (cyclohexane/EtOAc: 80/20) afforded 165 mg (17%) of an inseparable mixture of 3c and 3c (75/25 ratio) and 574mg (60%) of 3c. (1S*,2S*)-2-[(Bromomercurio)methyl]-3-hydroxy-1-((1S*)-2-hydroxy-1-methylethyl) propyl 2,2-dimethylpropanoate 3c. 1H NMR d 4.96 (dd, J = 8.8 and 3.7 Hz, 1H), 3.63 (dd, J = 9.9 and 5.1 Hz, 1H), 3.57-3.40 (m, 3H+OH), 2.73 (br s, 1H, OH), 2.46 (m, 1H), 2.00 (m, 1H), 1.97 (dd, J = 11.9 and 4.0 Hz, 1H), 1.76 (dd, J = 11.9 and 9.0 Hz, 1H), 1.25 (s, 9H), 1.03 (d, J = 7.0 Hz, 3H); 13C NMR d 179.5 (s), 75.4 (d), 65.1 (t), 63.6 (t), 41.3 (d), 39.2 (s), 36.8 (d), 28.7 (t), 27.4 (q, 3C), 14.1 (q). (2S*,3S*,4S*)-4-[(Bromomercurio)methyl]-3,5-dihydroxy-2-methylpentyl 2,2-dimethyl-propanoate 3 c. 1H NMR d 4.34 (dd, J = 11.0 and 4.8 Hz, 1H), 4.07 (dd, J = 11.0 and 4.0 Hz, 1H), 3.87-3.62 (m, 3H), 2.39 (m, 1H), 2.01-1.89 (m, 1H), 1.79-1.58 (m, 2H), 1.22 (s, 9H), 0.95 (d, J = 7.0 Hz, 3H); 13C NMR d 179.6 (s), 73.2 (d), 67.4 (t), 66.9 (t), 40.2 (d), 38.9 (s), 36.4 (d), 27.2 (q, 3C), 25.5 (t), 13.8 (q). (2S*,3R*,4S*)-4-[(Bromomercurio)methyl]-3,5-dihydroxy-2-methylpentyl 2,2-dimethyl-propanoate 3 c. 1H NMR d 4.16 (dd, J = 11.0 and 7.3 Hz, 1H), 3.97 (dd, J = 11.0 and 6.1 Hz, 1H), 3.87-3.62 (m, 3H), 2.66 (m, 1H), 2.01-1.89 (m, 1H), 1.79-1.58 (m, 2H), 1.22 (s, 9H), 0.83 (d, J = 7.0 Hz, 3H); 13C NMR d 179.1 (s), 75.0 (d), 68.4 (t), 67.4 (t), 39.4 (d), 38.8 (s), 36.7 (d), 27.2 (q, 3C), 26.1 (t), 13.2 (q). Reductive demercuration of 3c, 3 c and 3 c. According to the representative procedure, reductive demercuration of 3c (570 mg, 1.11 mmol) with n-Bu3SnH (600 mL, 2.22 mmol) and a catalytic amount of AIBN (2 mg) in THF (5 mL), and purification by flash chromatography (cyclohexane/EtOAc: 60/40 to 40/60) afforded 227 mg (88%) of 4b as a colorless oil. Similarly, reductive demercuration of 3 c and 3 c (75/25 mixture, 165 mg, 0.32 mmol) with n-Bu3SnH (170 mL, 0.64 mmol) and a catalytic amount of AIBN (2 mg) in THF (5 mL), afforded after purification by flash chromatography (cyclohexane/EtOAc: 60/40 to 40/60), 52 mg (70%) of a mixture of 4 c and 4 b (75/25 ratio). (2S*,3R*,4S*)-3,5-Dihydroxy-2,4-dimethylpentyl 2,2-dimethylpropanoate 4 c. IR 3400, 1730, 1710, 1290, 1170, 1030 cm-1; 1H NMR d 4.35 (dd, J = 11.0 and 5.2 Hz, 1H), 4.09 (dd, J = 11.0 and 3.7 Hz, 1H), 3.78-3.60 (m, 2H+OH), 3.56 (dd, J = 9.7 and 2.0 Hz, 1H), 3.39 (br s, 1H, OH), 2.03-1.73 (m, 2H), 1.22 (s, 9H), 0.95 (d, J = 7.0 Hz, 3H), 0.91 (d, J = 7.0 Hz, 3H); 13C NMR d 179.4 (s), 74.5 (d), 67.5 (t), 67.0 (t), 38.9 (s), 36.7 (d), 35.7 (d), 27.2 (q, 3C), 13.7 (q), 8.5 (q). Preparation of compounds 7a 7d. Preparation of cyclopropanes 7a and 7b. Cyclopropanes 7a and 7b were prepared by hydroboration of isopropenylcyclopropane 9,1, followed by esterification of the primary alcohol moiety with pivaloyl chloride (Scheme 1).  Scheme 1 Hydroboration of isopropenylcyclopropane 9. To a solution of 9 (340 mg, 1.68 mmol) in THF (5 mL) at -30 C, was added BH3.THF complex (1.68 mL, 1M in THF, 1.68 mmol) and the reaction mixture was allowed to warm to rt for 1 h. After 1 h, a 6M aqueous solution of NaOH (5 mL) and a 30% aqueous H2O2 solution (5 mL) were successively added dropwise at 0 C. After 3 h at rt, the aqueous phase was extracted with ether, the combined organic extracts were washed with brine, dried over MgSO4 and concentrated under reduced pressure. Purification of the crude material by flash chromatography (cyclohexane/EtOAc: 80/20) afforded 144 mg (39%) of 10a (less polar diastereomer) and 92 mg (25%) of 10b (more polar diastereomer), as colorless oils. (2R*)-2-{(1R*,2S*)-2-[(Benzyloxy)methyl]cyclopropyl}propan-1-ol 10a. Rf (cyclohexane/EtOAc: 50/50) = 0.42; IR 3430, 1095, 1070, 1030 cm1; 1H NMR d 7.38-7.23 (m, 5H), 4.55 (d, J = 12.2 Hz, 1H), 4.47 (d, J = 12.2 Hz, 1H), 3.73 (dd, J = 9.5 and 5.3 Hz, 1H), 3.62-3.46 (m, 2H), 3.25 (br s, 1H, OH), 2.86 (dd apparent t, J = 9.5 Hz, 1H), 1.14-0.94 (m, 3H), 0.90 (d, J = 6.4 Hz, 3H), 0.40-0.28 (m, 2H); 13C NMR d 138.1 (s), 128.3 (d, 2C), 127.5 (d), 127.4 (d, 2C), 74.3 (t), 72.7 (t), 69.1 (t), 40.0 (d), 21.7 (d), 18.1 (d), 16.4 (q), 7.1 (t); EI MS m/z (relative intensity) 161 (M+-CH3CHCH2OH, 4), 108 (11), 107 (13), 92 (15), 91 (100), 82 (10). (2S*)-2-{(1R*,2S*)-2-[(Benzyloxy)methyl]cyclopropyl}propan-1-ol 10b. Rf (cyclohexane/EtOAc: 50/50) = 0.22; IR 3400, 3080, 1090, 1070, 1030 cm-1; 1H NMR d 7.40-7.24 (m, 5H), 4.55 (d, J = 12.1 Hz, 1H), 4.50 (d, J = 12.1 Hz, 1H), 3.54 (d, J = 5.9 Hz, 2H), 3.40 (dd, J = 10.0 and 6.6 Hz, 1H), 3.24 (dd, J = 10.0 and 7.4 Hz, 1H), 2.16 (br s, 1H, OH), 1.24 (m, 1H), 0.93 (m, 1H), 0.92 (d, J = 6.8 Hz, 3H), 0.55-0.49 (m, 2H), 0.42 (m, 1H); 13C NMR d 138.4 (s), 128.3 (d, 2C), 127.5 (d, 2C), 127.4 (d), 74.2 (t), 72.4 (t), 68.3 (t), 38.6 (d), 20.3 (d), 15.4 (q), 15.3 (d), 9.0 (t); EI MS m/z (relative intensity) 161 (M+-CH3CHCH2OH, 3), 108 (12), 92 (15), 91 (100), 82 (10). (2R*)-2-{(1S*,2S*)-2-[(Benzyloxy)methyl]cyclopropyl}propyl 2,2-dimethylpropanoate 7a. To a solution of 10a (460 mg, 2.09 mmol) and DMAP (383 mg, 3.13 mmol) in CH2Cl2 (10 mL) was added pivaloyl chloride (310 mL, 2.50 mmol). After 2 h at rt, the reaction mixture was quenched with MeOH (1 mL). After 20 min, an aqueous saturated NaHCO3 solution was added and the resulting mixture was extracted with ether. The combined extracts were dried over MgSO4 and concentrated under reduced pressure. Purification by flash chromatography (cyclohexane/EtOAc: 95/5) afforded 614 mg (96%) of 7a as a colorless oil; IR 3060, 1725, 1480, 1290, 1160, 1095 cm-1; 1H NMR d 7.36-7.23 (m, 5H), 4.50 (s, 2H), 4.07 (dd, J = 10.8 and 5.5 Hz, 1H), 3.95 (dd, J = 10.8 and 6.8 Hz, 1H), 3.45 (dd, J = 10.1 and 6.1 Hz, 1H), 3.16 (dd, J = 10.1 and 7.5 Hz, 1H), 1.19 (m, 1H), 1.19 (s, 9H), 0.98 (d, J = 6.6 Hz, 3H), 0.98 (m, 1H), 0.54-0.36 (m, 3H); 13C NMR d 178.4 (s), 138.5 (s), 128.3 (d, 2C), 127.5 (d, 2C), 127.4 (d), 73.7 (t), 72.4 (t), 69.1 (t), 38.7 (s), 37.2 (d), 27.2 (q), 20.5 (d), 17.5 (d), 16.5 (q), 8.9 (t); EI MS m/z (relative intensity) 213 (M+-CH2Ph, 1), 96 (22), 95 (17), 92 (12), 91 (100), 81 (16), 57 (37). Anal. Calcd for C19H28O3: C, 74.96; H, 9.27. Found: C, 74.81; H, 9.37. (2S*)-2-{(1S*,2S*)-2-[(Benzyloxy)methyl]cyclopropyl}propyl 2,2-dimethylpropanoate 7b. Following the procedure described for the preparation of 7a from 10a, esterification of 10b (100 mg, 0.44 mmol) with pivaloyl chloride (67 (L, 0.54 mmol) and DMAP (83 mg, 0.68 mmol) in CH2Cl2 (5 mL), followed by flash chromatography (cyclohexane/EtOAc: 95/5) afforded 129 mg (93%) of 7b as a colorless oil; IR 3060, 1730, 1285, 1165, 1100 cm-1; 1H NMR d 7.35-7.25 (m, 5H), 4.56 (d, J = 12.0 Hz, 1H), 4.49 (d, J = 12.0 Hz, 1H), 4.07 (dd, J = 10.8 and 5.5 Hz, 1H), 3.90 (dd, J = 10.8 and 6.8 Hz, 1H), 3.38 (dd, J = 10.3 and 6.6 Hz, 1H), 3.27 (dd, J = 10.3 and 7.0 Hz, 1H), 1.21 (m, 1H), 1.20 (s, 9H), 1.04 (d, J = 6.6 Hz, 3H), 0.93 (m, 1H), 0.52-0.39 (m, 3H); 13C NMR d 178.5 (s), 138.6 (s), 128.3 (d, 2C), 127.5 (d, 2C), 127.4 (d, 1C), 74.0 (t), 72.4 (t), 69.0 (t), 38.8 (s), 37.3 (d), 27.2 (q, 3C), 20.8 (d), 16.8 (q), 16.7 (d), 9.8 (t); EI MS m/z (relative intensity) 304 (M+, 1), 247 (M+-t-Bu, 1), 197 (15), 96 (11), 95 (21), 92 (13), 91 (100), 57 (37). Anal. Calcd for C19H28O3: C, 74.96; H, 9.27. Found: C, 74.82; H, 9.42. Preparation of cyclopropane 7c Cyclopropane 7c was prepared from isopropenylcyclopropane 11 (Scheme 2).1,3  Scheme 2 (2R*)-2-{(1R*,2R*)-2-[(Benzyloxy)methyl]cyclopropyl}propan-1-ol 12. To a solution of isopropenylcyclopropane 11 in dry THF (5 mL) at -30 C, was added BH3.THF complex (3 mL, 1M in THF, 3 mmol). The reaction mixture was warmed to 20 C for 1 h. After 1 h, a 6M aqueous NaOH solution (10 mL) and a 30% aqueous H2O2 solution (10 mL) were successively added dropwise at 0 C. After 3 h at 20 C, the aqueous phase was extracted with ether, the combined extracts were washed with brine, dried over MgSO4 and concentrated under reduced pressure. Purification of the crude material by flash chromatography (cyclohexane/EtOAc: 80/20) afforded 150 mg (66%) of 12 as a colorless oil; IR 3420, 3060, 1090, 1070 cm-1; 1H NMR d 7.40-7.24 (m, 5H), 4.51 (s, 2H), 3.80 (br s, 1H, OH), 3.80 (dd, J = 10.4, 5.1 Hz, 1H), 3.57 (dd, J = 10.4 and 4.5 Hz, 1H), 3.43 (dd apparent t, J = 10.0 Hz, 1H), 3.11 (dd apparent t, J = 10.0 Hz, 1H), 1.34-1.18 (m, 2H), 0.96 (d, J = 6.8 Hz, 3H), 0.73-0.59 (m, 2H), -0.11 (m, 1H); 13C NMR d 137.4 (s), 128.3 (d, 2C), 127.8 (d, 2C), 127.7 (d), 72.9 (t), 70.4 (t), 68.8 (t), 35.1 (d), 21.1 (d), 17.7 (q), 16.2 (d), 6.3 (t); EI MS m/z (relative intensity) 143 (M+-Ph, 2), 108 (9), 107 (11), 92 (15), 91 (100), 82 (9), 81 (10), 67 (10), 55 (9). (2R*)-2-{(1S*,2R*)-2-[(Benzyloxy)methyl]cyclopropyl}propyl 2,2-dimethylpropanoate 7c. To a solution of 12 (140 mg, 0.636 mmol) and DMAP (116 mg, 0.949 mmol) in CH2Cl2 (5mL) was added pivaloyl chloride (94 (L, 0.76 mmol). After 2 h at 20 C, the reaction mixture was quenched with MeOH (1 mL). After 20 min, an aqueous saturated NaHCO3 solution was added, and the resulting mixture was extracted with ether. The combined extracts were dried over MgSO4 and concentrated under reduced pressure. Purification of the crude material by flash chromatography (cyclohexane/EtOAc: 95/5) afforded 172 mg (90%) of 7c as a colorless oil; IR 3060, 1725, 1285, 1165 cm-1; 1H NMR d 7.26-7.15 (m, 5H), 4.47 (d, J = 11.8 Hz, 1H), 4.42 (d, J = 11.8 Hz, 1H), 4.17 (dd, J = 10.6 and 4.1 Hz, 1H), 3.82 (dd, J = 10.6 and 8.1 Hz, 1H), 3.45 (dd, J = 10.1 and 6.9 Hz, 1H), 3.39 (dd, J = 10.1 and 7.9 Hz, 1H), 1.31 (m, 1H), 1.17 (s, 9H), 1.13 (m, 1H), 0.97 (d, J = 6.7 Hz, 3H), 0.77-0.64 (m, 2H), -0.04 (m, 1H); 13C NMR d 178.4 (s), 138.4 (s), 128.3 (d, 2C), 127.8 (d, 2C), 127.5 (d), 72.8 (t), 70.5 (t), 69.1 (t), 38.8 (s), 32.8 (d), 27.2 (q, 3C), 19.7 (d), 17.6 (q), 16.1 (d), 8.3 (t); EI MS m/z (relative intensity) 219 (M+-t-BuCO, 1), 213 (M+-CH2Ph, 1), 96 (25), 95 (16), 92 (12), 91 (100), 81 (19), 57 (40). Anal. Calcd for C19H28O3: C, 74.96; H, 9.27. Found: C, 74.81; H, 9.39. Preparation of cyclopropane 7d Compound 7d was prepared from isopropenylcyclopropane 131,3 according to Scheme 3. Scheme 3 2-((1S*,2R*)-2-{[(tert-Butyldiphenylsilyl)oxy]methyl}cyclopropyl)prop-2-en-1-ol 14. To a solution of SeO2 (411 mg, 3.71 mmol, 0.5 equiv.) in CH2Cl2 (120 mL) at 0 C, was added tert-butyl hydroperoxide (2.70 mL, ca 5.5M in decane, 14.8 mmol, 2.0 equiv.). After 30 min, a solution of 13 (2.60 g, 7.42 mmol) in CH2Cl2 (30 mL) was added dropwise and the reaction mixture was allowed to warm to rt. After 12 h, the reaction mixture was quenched with a 1M aqueous NaOH solution and extracted with CH2Cl2. The combined extracts were washed with brine, dried over MgSO4 and concentrated under reduced pressure to give a yellow oil, which was dissolved in MeOH (60 mL). To the solution was added CeCl3.7H2O (1.93 g, 5.19 mmol, 0.7 equiv.), followed by the addition of sodium borohydride (196 mg, 5.19 mmol, 0.7 equiv.) portionwise at 0 C. After 20 min, the reaction mixture was poured into a 1M aqueous HCl solution and extracted with Et2O. The combined extracts were washed with brine, dried over MgSO4, concentrated under reduced pressure and the crude material was purified by flash chromatography (petroleum ether/EtOAc: 90/10 to 85/15) to give 1.95 g (74%) of 14 as a colorless oil; IR 3300, 1110 cm-1; 1H NMR d 7.72-7.62 (m, 4H), 7.47-7.35 (m, 6H), 5.14 (t, J = 0.7 Hz, 1H), 4.67 (s, 1H), 4.30 (d, J = 5.3 Hz, 2H), 3.83 (dd, J = 10.9 and 4.0 Hz, 1H), 3.46 (t, J = 5.3 Hz, 1H, OH), 3.17 (dd apparent t, J = 10.9 Hz, 1H), 1.68 (m, 1H), 1.42 (m, 1H), 1.04 (s, 9H), 0.69 (m, 1H), 0.40 (m, 1H); 13C NMR d 146.0 (s), 135.6 (d), 135.5 (d), 133.1 (s, 2C), 129.8 (d, 2C), 129.7 (d, 2C), 127.7 (d, 4C), 110.9 (t), 67.7 (t), 63.1 (t), 26.7 (q, 3C), 19.8 (d), 19.3 (d), 19.0 (s), 4.7 (t); EI MS m/z (relative intensity) 309 (M+-t-Bu, 2), 199 (100), 18 (11), 139 (27), 93 (10). Anal. Calcd for C23H30O2Si: C, 75.36; H, 8.25. Found: C, 75.31; H, 8.35. (2S*)-2-((1R*,2R*)-2-{[(tert-Butyldiphenylsilyl)oxy]methyl}cyclopropyl)propan-1-ol 15. To a solution of 14 (300 mg, 0.819 mmol) and potassium azodicarboxylate (7.9 g, 41 mmol, 50 equiv.) in MeOH (50 mL) at 40 C, was added acetic acid (4.7 mL, 82 mmol, 100 equiv.) via syringe pump over 2h. After 1h at 40 C, the same quantities of potassium azodicarboxylate and acetic acid were added to the reaction mixture under similar conditions. After 1h at 40 C, the reaction mixture was concentrated under reduced pressure and the solid residue was suspended in ether (250 mL). Triethylamine (10 mL) was added and the resulting mixture was filtered through Celite. The insoluble salts were thoroughly washed with ether and the filtrate was concentrated under reduced pressure. The crude material was purified by flash chromatography (cyclohexane/EtOAc: 80/20 to 70/30) to give 207 mg (69%) of 15 as a colorless oil; IR 3350, 1110, 1070, 1030 cm-1; 1H NMR d 7.72-7.66 (m, 4H), 7.46-7.35 (m, 6H), 3.77 (dd, J = 11.3 and 5.9 Hz, 1H), 3.64-3.47 (m, 2H) 3.56 (dd, J = 11.3 and 8.5 Hz, 1H), 1.42 (s, 1H, OH), 1.22 (m, 1H), 1.13 (m, 1H), 1.12 (d, J = 6.6 Hz, 3H), 1.05 (s, 9H), 0.67-0.60 (m, 2H), -0.01 (m, 1H); 13C NMR d 135.6 (d, 2C), 135.5 (d, 2C), 133.9 (s), 133.8 (s), 129.5 (d, 2C), 127.6 (d, 2C), 127.5 (d, 2C), 68.9 (t), 64.0 (t), 35.6 (d), 26.8 (q, 3C), 20.0 (d), 19.1 (s) , 17.5 (q), 16.6 (d), 7.8 (t); EI MS m/z (relative intensity) 311 (M+-t-Bu, 19), 200 (20), 199 (100), 183 (10), 181 (12), 139 (15), 69 (15). (2S*)-2-[(1S*,2R*)-2-(Hydroxymethyl)cyclopropyl]propyl 2,2-dimethylpropanoate 16. To a solution of 15 (180 mg, 0.489 mmol) and DMAP (89 mg, 0.73 mmol) in CH2Cl2 (10mL) was added pivaloyl chloride (72 (L, 0.58 mmol). After 2 h at 20 C, the reaction mixture was quenched with MeOH (1 mL). After 20 min, an aqueous saturated NaHCO3 solution was added and the resulting mixture was extracted with ether. The combined extracts were dried over MgSO4 and concentrated under reduced pressure, to give an oil which was dissolved in THF (5 mL). To the resulting solution at 0 C, was added tetrabutylammonium fluoride (1.50 mL, 1M in THF, 1.50 mmol). After 3 h at 20 C, the reaction mixture was poured into an aqueous saturated NH4Cl solution and extracted with ether. The combined extracts were dried over MgSO4 and concentrated under reduced pressure. Purification by flash chromatography (pentane/ether: 80/20) afforded 106 mg of 16, slightly contaminated by tributylamine; IR 3400, 1730, 1290, 1165, 1030 cm-1; 1H NMR d 4.11 (dd, J = 10.7 and 5.5 Hz, 1H), 3.93 (dd, J = 10.7 and 7.0 Hz, 1H), 3.68 (dd, J = 11.0 and 7.4 Hz, 1H), 3.61 (dd, J = 11.0 and 7.4 Hz, 1H), 2.11 (br s, 1H, OH), 1.40 (m, 1H), 1.22 (m, 1H), 1.21 (s, 9H), 1.08 (d, J = 6.6 Hz, 3H), 0.76-0.70 (m, 2H), 0.12 (m, 1H); 13C NMR d 178.6 (s), 69.5 (t), 62.6 (t), 38.7 (s), 33.1 (d), 27.1 (q, 3C), 20.1 (d), 17.8 (q), 17.3 (d), 8.5 (t). (2S*)-2-{(1S*,2R*)-2-[(Benzyloxy)methyl]cyclopropyl}propyl 2,2-dimethylpropanoate 7d To a solution of 16 (106 mg, ca 0.46 mmol) and DMAP (11 mg, 0.093 mmol) in dry ether (5mL) was added chlorotrimethylsilane (72 (L, 0.56 mmol). After 10 min at 20 C, pentane was added and the reaction mixture was filtered through Celite. The filtrate was concentrated under reduced pressure to give a yellow oil, which was dissolved in CH2Cl2 (10 mL). To the resulting solution were added benzaldehyde (60 (L, 0.59 mmol) and triethylsilane (110 mL, 0.681 mmol). The reaction mixture was cooled to -78C, and trimethylsilyl trifluoromethanesulfonate (10 (L, 0.046 mmol, 0.01 equiv) was added. After 30 min at 78C, the reaction mixture was poured into an aqueous saturated NaHCO3 solution and extracted with ether. The combined extracts were washed with brine, dried over MgSO4 and concentrated under reduced pressure. Purification by flash chromatography (pentane/ether: 95/5) afforded 125 mg (88% from 15) of 7d as a colorless oil; IR 3070, 1730, 1290, 1165, 1090 cm-1; 1H NMR d 7.35-7.25 (m, 5H), 4.56 (d, J = 12.0 Hz, 1H), 4.49 (d, J = 12.0 Hz, 1H), 4.09 (dd, J = 10.7 and 5.5 Hz, 1H), 3.91 (dd, J = 10.7 and 7.0 Hz, 1H), 3.54 (dd, J = 10.3 and 6.3 Hz, 1H), 3.40 (dd, J = 10.3 and 8.1 Hz, 1H), 1.42-1.14 (m, 2H), 1.20 (s, 9H), 1.09 (d, J = 6.6 Hz, 3H), 0.78-0.64 (m, 2H), 0.10 (m, 1H); 13C NMR d 178.5 (s), 138.4 (s), 128.3 (d, 2C), 127.6 (d, 2C), 127.5 (d), 72.8 (t), 70.2 (t), 69.6 (t), 38.7 (s), 33.1 (d), 27.2 (q, 3C), 19.8 (d), 17.6 (q), 14.6 (d), 8.7 (t); EI MS m/z (relative intensity) 304 (M+, 1), 247 (M+-t-Bu, 1), 197 (20), 95 (23), 92 (13), 91 (100), 57 (38). Anal. Calcd for C19H28O3: C, 74.96; H, 9.27. Found: C, 74.79; H, 9.39. Oxymercuration of benzylethers 7a-7d: representative procedure To a solution of 7a (200 mg, 0.657 mmol) in CH2Cl2 (7 mL) was added mercuric trifluoroacetate (560mg, 1.31 mmol). After 1 h at 20 C, with complete exclusion of light, the reaction mixture was hydrolyzed with a saturated aqueous KBr solution and extracted with CH2Cl2. The combined extracts were dried over MgSO4, concentrated under reduced pressure to give a white oil, which was dissolved in THF (10 mL). To the resulting solution was added a catalytic amount of AIBN (2 mg) and n-Bu3SnH (210 mL, 0.781 mmol). Mercury began to precipitate instantaneously and after 30 min at rt, the reaction mixture was hydrolyzed with a 20% aqueous KF solution (1 mL). After 30 min, the resulting mixture was diluted with EtOAc, filtered through Celite, and the filtrate was extracted with EtOAc. The combined extracts were dried over MgSO4, concentrated under reduced pressure to give an oil, which was dissolved in THF (10 mL). To the resulting solution at 0 C, was added LiAlH4 (30 mg, 0.78 mmol) in one portion. After 2 h at rt, the reaction mixture was successively treated with water (0.1 mL), a 15% aqueous NaOH solution (0.1 mL) and water (0.3 mL). After 2 h at 20C, the reaction mixture was filtered through Celite and concentrated under reduced pressure. Purification by flash chromatography (cyclohexane/EtOAc: 50/50) afforded 40 mg (38%) of 8a, as a colorless oil. According to this procedure, 7b, 7c and 7d were respectively converted to the known stereotriads 8b4,5 (50%), 8c4 (65%) and 8d (47%) .  Cossy, J.; Blanchard, N.; Hamel, C; Meyer, C. J. Org. Chem. 1999, 64, 2608.  Cossy, J.; Blanchard, N.; Meyer, C. Synthesis 1999, 1063.  For the preparation of isopropenylcyclopropanes, see: Cossy, J.; Blanchard, N.; Meyer, C. Eur. J. Org. Chem. 2001, 339.  Nagaoka, H.; Kishi, Y. Tetrahedron 1981, 23, 3873.  Gennari, C.; Colombo, L.; Bertolini, G.; Schimperna, G. J. Org. Chem. 1987, 52, 2754.  Yokoyama, Y.; Terada, Y.; Kawashima, H. Bull. Chem. Soc. Jpn. 1991, 61, 2563.  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