ࡱ> S Ԇbjbj "xxi lX@000D&&&&|D$Y2p:::::4 WWWWWWW$VZ v\vW08 ::8 8 W000::X0008 0:0:W08 W0 0:RGTl00{W: 0j6BD&%U{WDX0$YU\+\{W0DD0000Supporting Information for Substituted Alkyne Synthesis Under Non-basic Conditions Copper Carboxylate-mediated, Palladium-catalyzed ThioalkyneBoronic Acid Cross-Coupling by Cecile Savarin, Jiri Srogl*, and Lanny S. Liebeskind* Sanford S. Atwood Chemistry Center, Emory University 1515 Pierce Drive, Atlanta, GA, 30322 General Methods 1H, 13C and 19F NMR spectra were recorded on a Varian Mercury 300 MHz (300 MHz 1H, 75.0 MHz 13C) or Varian Inova 400 MHz (400 MHz 1H, 100.0 MHz 13C, 376.3 MHz 19F) spectrometer in deuteriochloroform (CDCl3) or deuterio-DMSO ((CD6)2SO) with either tetramethylsilane (TMS) (0.00 ppm 1H, 0.00 ppm) or chloroform (7.26 ppm 1H, 77.00 ppm) or DMSO (2.50 ppm, 1H) or DMS (2.09 ppm, 1H) as internal reference unless otherwise stated. 19F NMR spectra were referenced with trifluoromethyltoluene in benzene (-63.7 ppm) as external standard. 31P NMR spectra were referenced with 85% H3PO4 in benzene (0.0 ppm) as external standard. Data are reported in the following order: chemical shifts are given ((); multiplicities are indicated (br (broadened), s (singlet), d (doublet), t (triplet), q (quartet), pent (pentuplet), hex (hextet), hept (heptet), m (multiplet), exch (exchangeable), app (apparent)); coupling constants, J, are reported (Hz); integration is provided. Infrared spectra were recorded on a Nicolet 510 FT-IR spectrometer with a resolution of 4 cm-1 or ASI ReactIR 1000FT-IR spectrometer with a silicone probe. Peaks are reported (cm-1) with the following relative intensities: s (strong, 67-100%), m (medium, 40-67%), w (weak, 20-40%) and br (broad). GC-MS spectra were recorded on a Shimadzu Gas Chromatograph GC-17A, Mass Spectrometer QP-5000. GC/MS analysis was carried out on a bonded 5% diphenylsiloxane capillary column (30 m, 0.25 mm id, 0.25 (m df). Elementary analyses were performed by Atlantic Microlab, Inc., Norcross, Georgia. Melting points were taken on a Thomas-Hoover melting point apparatus in open capillary tubes and are uncorrected. Analytical thin-layer chromatography (TLC) was performed on Merck silica gel 60 plates, 0.25 mm thick with F-254 indicator. Visualization was accomplished by UV light, 5% phosphomolybdic acid solution in ethanol. Flash column chromatography was performed by the method of Still with 32-63 (m silica gel (Woelm). Rotatory chromatography was performed with a Chromatotron"! from Harrison Research using 4 mm PF-254 silica rotors. Preparative plate chromatography was performed on Merck silica gel 60 plates, 0.5 mm thick with F-254 indicator. Solvents for extraction and chromatography were reagent grade and used as received. Dried solvents (THF, toluene, CH3CN, benzene, DMA) used as reaction media were purchased from Aldrich and dried over 4A molecular sieves and titrated for water level prior to use with a Fisher Coulomatic K-F titrator. Et3N and pyridine were dried over 4A molecular sieves. All solvents, unless otherwise noted were sparged with nitrogen for several hr. All reactions were performed under a dry nitrogen in oven- and/or flame-dried glassware, except for those reactions utilizing water as a solvent, which were run under air. Brine refers to a saturated aqueous solution of NaCl. Unless otherwise specified, solutions of HCl, NH4Cl, NaHCO3 refer to aqueous solutions. Starting Materials N-Chlorosuccinimide, thiocresol, methyldisulfide, 3-methylsalicylic acid, thiophene-2-carboxylic acid, phenylboronic acid, Cu2O, Pd(dppf)Cl2, Pd(PPh3)4, Pd(OAc)2 P(o-tolyl)3, P(OEt)3, n-BuLi (1.4-1.6 M in hexanes), ethynylmagnesium chloride (0.5 M in THF), ethynylbenzene, (cyclohex-1-enyl)ethyne, propynoic acid ethyl ester, hex-1-yne, and 17-ethynyl-3-methoxy-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-17-ol, 3-methoxypropyne were purchased from Aldrich Chemical Co. and used as received. Boronic acid reagents were obtained from Frontier Scientific. CuTC was prepared as previously described. Copper (I)-3-methylsalicylate, CuMeSal. Cu2O (6.9 g, 0.09 mol of Cu, 1.0 equiv) and 3-methylsalicylic acid (23.0 g, 0.15 mol, 1.6 equiv) were introduced into a 1000 mL round-bottomed flask, which was equipped with a Dean-Stark apparatus. Under argon, dry and degassed toluene (200 mL) was added and the mixture was refluxed for 2 days. CuMeSal was filtered under argon, washed with dry and degassed toluene (2 x 100 mL), MeOH (50 mL), ether (200 mL) and dried for 2 h. CuMeSal (16.7 g, 0.08 mol, 88%) was obtained as a beige powder. Mp 205 oC (decomp). IR (KBr pellet, cm-1): 3210 (br), 1873 (s), 1734 (s), 1597 (s). 1H NMR (d6 DMS, 400 MHz): 14.35 (br s, 1 H), 7.75 (d, J = 6.8 Hz,1 H), 7.08 (d, J = 6.4 Hz,1 H), 6.58 (t, J = 6.8 Hz, 1 H), 2.21 (s, 3 H). Anal. Calcd for C8H7O3Cu: C, 44.75; H, 3.29; O, 22.36; Found: C, 44.55; H, 3.18; O, 22.22. N-(p-Tolylthio)succinimide was prepared by a literature procedure. TLC (CH2Cl2-ethanol, 20:1, Rf =0.74) Mp 111-112 oC (ethanol; lit.{113 oC, NOTEREF _Ref497276890 \f \h 2 114-115 oC }; IR (CCl4, KCl, cm-1): 2914 (w), 2848 (m), 1731 (s). 1H NMR (CDCl3, 400 MHz): 7.59 (d, J = 8.4 Hz, 2 H), 7.15 (d, J = 8.4 Hz, 2 H), 2.78 (s, 3 H), 2.24 (s, 4 H). (Hex-1-ynyl)methyl sulfide, 1 was prepared by the procedure of Narasaka. Bp 95 oC (7 mm Hg, short-path distillation); IR (neat, KCl, cm-1): 2197 (w). 1H NMR (CDCl3, 300 MHz): 2.29 (s, 3 H), 2.24 (t, J = 7.2 Hz, 2 H), 1.44-1.34 (m, 4 H), 0.86 (t, J = 7.2 Hz, 3 H). preparation of thioalkyne derivatives. General Procedure. The terminal alkyne (1.0 equiv) in dry and degassed THF was treated with n-BuLi (1.4-1.6 M in hexanes, 1.0-1.1 equiv) at -78 oC under argon for 30-90 min. p-Tolylthiosuccinimide (1.0-1.1 equiv) in dry and degassed THF was then added to the reaction mixture at -78 oC. After warming to room temperature, the reaction was monitored by TLC and GC/MS analysis. Upon completion of the reaction, hexanes was added to the reaction mixture, which was then filtered (except for thioalkyne 7, see details). The filtrate was evaporated to dryness to afford the desired product. Most were of sufficient purity for subsequent use, but some of the products needed aqueous work-up and/or further purification by chromatography. (Chromatotron"!, 4mm thick plate of silica gel, hexanes as eluent). The reaction time and conditions were not optimized, and reactions were run only once. (Phenylethynyl) (p-tolyl) sulfide, 2. Following the typical procedure, ethynylbenzene (702 mg, 6.9 mmol, 1.0 equiv) in THF (12 mL) was treated at -78 oC with 1.6 M n-BuLi (4.20 mL, 6.7 mmol, 1.0 equiv) for 90 min, and then p-tolylthiosuccinimide (1.50 g, 6.8 mmol, 1.0 equiv) in THF (10 mL) was added. After addition of hexanes (70 mL), filtration of the reaction mixture, and evaporation of the filtrate to dryness, 2 (1.32 g, 5.9 mmol, 88 %) was obtained as a white solid. TLC (hexanes, Rf = 0.45); Mp 46-47 oC (ethanol; lit.{45-46 oC5b}); IR (neat, cm-1): 2171 (m), 1596 (m). 1H NMR (CDCl3, 400 MHz): 7.53-7.51 (m, 2 H), 7.40 (d, J = 8.0 Hz, 2 H), 7.36-7.34 (m, 3 H), 7.18 (d, J = 8.0 Hz, 2 H), 2.36 (s, 3 H). (3-Methoxyprop-1-ynyl)- p-tolyl sulfide, 3. Following the typical procedure, 3-methoxypropyne (0.58 mL, 6.9 mmol, 1.0 equiv) in THF (12 mL) was treated at -78 oC with 1.6 M n-BuLi (4.20 mL, 6.7 mmol, 1.0 equiv) for 90 min, and then p-tolylthiosuccinimide (1.50 g, 6.8 mmol, 1.0 equiv) in THF (10 mL) was added. After addition of hexanes (70 mL), filtration of the reaction mixture, and evaporation of the filtrate to dryness, 3 (1.13 g, 5.9 mmol, 85 %) was obtained as a colorless oil. TLC (hexanes-ether, 2:1, Rf = 0.58); IR (neat, KCl, cm-1): 2182 (m). 1H NMR (CDCl3, 400 MHz): 7.32 (d, J = 8.0 Hz, 2 H), 7.15 (d, J = 8.0 Hz, 2 H), 4.32 (s, 2 H), 3.42 (s, 3 H), 2.33 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 136.8, 130.0, 128.6, 126.7, 94.5, 74.2, 60.7, 57.5, 21.0. 3-(p-Tolylthio)propynoic acid ethyl ester 4. Following the typical procedure, propynoic acid ethyl ester (0.5 mL, 4.9 mmol, 1.0 equiv) in THF (13 mL) was treated at -78 oC with 1.6 M n-BuLi (2.95 mL, 4.7 mmol, 1.0 equiv) for 75 min, and then p-tolylthiosuccinimide (1.09 g, 4.9 mmol, 1.0 equiv) in THF (7 mL) was added. After addition of hexanes (80 mL), filtration of the reaction mixture, evaporation of the filtrate to dryness, and chromatography by Chromatotron"! (hexanes), 4 (796 mg, 3.6 mmol, 73 %) was obtained as a colorless oil. TLC (hexanes-ether, 2:1, Rf = 0.67); IR (neat, KCl, cm-1): 2156 (s), 1706 (s). 1H NMR (CDCl3, 400 MHz): 7.36 (d, J = 8.4 Hz, 2 H), 7.19 (d, J = 8.0 Hz, 2 H), 4.26 (q, J = 7.2 Hz, 2 H), 2.35 (s, 3 H), 1.32 (t, J = 7.2 Hz, 3 H). 13C NMR (CDCl3, 100 MHz): 153.0, 138.2, 130.4, 127.9, 125.6, 90.9, 80.7, 61.9, 21.1, 14.1. Anal. Calcd for C12H12O2S: C, 65.43; H, 5.49; S, 14.56; Found: C, 65.50; H, 5.50; S, 14.33. Bis(p-tolylthio)ethyne 5. Ethynylmagnesium chloride (0.5 M in THF, 0.45 mL, 0.23 mmol, 1.0 equiv) was added to a solution of p-tolylthiosuccinimide (53 mg, 0.24 mmol, 1.0 equiv) in THF (1 mL) at 0 oC. After stirring for one hour at 0-5 oC, completion of the reaction was checked by TLC and GC/MS. Then, at 0 oC 1.4 M n-BuLi (0.17 mL, 0.24 mmol, 1.0 equiv) was added and, after stirring for 30 min at 0 oC, p-tolylthiosuccinimide (53 mg, 0.24 mmol, 1.0 equiv) was added. The reaction mixture was stirred for 2 hr and allowed to warm to room temperature. After addition of hexanes (20 mL), filtration of the reaction mixture, and evaporation of the filtrate to dryness, 5 (46 mg, 0.17 mmol, 75 %) was obtained as white needles. TLC (hexanes-ether, 2:1, Rf = 0.80); Mp 99-100 oC (ethanol; lit.{98-99 oC 7}); IR (CCl4, KCl, cm-1): 1905 (m). 1H NMR (CDCl3, 400 MHz): 7.34 (d, J = 8.0 Hz, 4 H), 7.16 (d, J = 8.0 Hz, 4 H), 2.33 (s, 6 H). [2-(Cyclohex-1-enyl)ethynyl] (p-tolyl) sulfide, 6. Following the typical procedure, (cyclohex-1-enyl)ethyne (0.52 mL, 4.6 mmol, 1.0 equiv) in THF (16 mL) was treated at -78 oC with 1.6M n-BuLi (3.0 mL, 4.8 mmol, 1.0 equiv) for 2 h, and then p-tolylthiosuccinimide (1.11 g, 5.0 mmol, 1.1 equiv) in THF (6 mL) was added. After addition of hexanes (50 mL), filtration of the reaction mixture, and evaporation of the filtrate to dryness, 6 (0.98 g, 4.3 mmol, 93 %) was obtained as a colorless oil. TLC (hexanes, Rf = 0.40); IR (neat, KCl, cm-1): 2146 (m), 1890 (m). 1H NMR (CDCl3, 400 MHz): 7.31 (dt, J = 8.0, 2.0 Hz, 2 H), 7.14 (d, J = 8.0 Hz, 2 H), 6.20 (pent, J = 2.0 Hz, 1 H), 2.32 (s, 3 H), 2.21-2.17 (m, 2 H), 2.16-2.11 (m, 2 H), 1.68-1.59 (m, 4 H). 13C NMR (CDCl3, 100 MHz): 136.1, 135.8, 129.8, 129.8, 126.1, 120.7, 99.4, 72.4, 29.1, 25.7, 22.2, 21.4, 20.9. Anal. Calcd for C15H16S: C, 78.90; H, 7.06; S, 14.04 Found: C, 79.00; H, 7.11; S, 13.91. 3-Methoxy-13-methyl-17-[(p-tolylthio)ethynyl]-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-17-ol, 7. 17-Ethynyl-3-methoxy-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-17-ol (101 mg, 0.33 mmol, 1.0 equiv) in THF (2 mL) was treated at -78 oC with 1.6 M n-BuLi (0.4 mL, 0.64 mmol, 2.0 equiv) for 120 min (-78 oC to -40 oC). Then p-tolylthiosuccinimide (102 mg, 0.46 mmol, 1.4 equiv) was added. After stirring for 2 h, the temperature was allowed to warm to room temperature and CH2Cl2 (40 mL) was added. The organic layer was extracted with 2N HCl (20 mL), dried (Na2SO4), filtered and evaporated. After chromatography (Chromatotron"!, CH2Cl2), 7 (100 mg, 0.23 mmol, 70 %) was obtained as white crystals. TLC (CH2Cl2, Rf = 0.52); Mp 58-59 oC; IR (neat, cm-1): 3435 (br, m), 2165 (w). 1H NMR (CDCl3, 400 MHz): 7.35 (d, J = 8.0 Hz, 2 H), 7.23 (d, J = 8.4 Hz, 1 H), 7.16 (d, J = 8.0 Hz, 2 H), 6.74 (dd, J = 8.4, 2.8 Hz, 1 H), 6.66 (d, J = 2.8 Hz, 1 H), 3.80 (s, 3 H), 2.90-2.86 (m, 2 H), 2.42-2.34 (m, 2 H), 2.35 (s, 3 H), 2.24-2.11 (m, 3 H), 1.91-1.76 (m, 5 H), 1.53-1.40 (m, 4 H), 0.94 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 157.4, 137.9, 136.5, 132.5, 130.0, 129.1, 126.3, 113.7, 111.4, 101.7, 81.0, 72.9, 55.1, 49.7, 47.7, 43.5, 39.4, 39.2, 33.1, 29.8, 27.2, 26.4, 22.9, 20.9, 12.8. LRMS (FAB): 432 ([M+], 76), 415 (100), 283 (37). HRMS (EI) Calcd for C28H32O2S: 432.2123. Found: 432.2112 ([M+], error -2.5 ppm). Anal. Calcd for C28H32O2S: C, 77.74; H, 7.46; S, 7.41; Found: C, 77.13; H, 7.39; S, 7.32. []25D = -41.6 (c 0.49 in CH2Cl2). Cross-Coupling of Thioalkyne Derivatives General Procedure. The organoboron reagent (1.0-1.5 equiv), Pd catalyst (3-10%), copper salt (CuTC, or CuMeSal, 1.0-1.5 equiv) and thioalkyne (1.0 equiv) were placed in a 25 mL Schlenk tube. After a vacuum and argon cycle, dry and degassed solvent was added. The reaction mixture was stirred for 3-18 h at 45-50 oC and monitored by GC/MS and TLC. When one of the starting materials was an oil, all the solids were first placed in a Schlenk tube, and after vacuum and argon cycle, the solvent was added followed by the addition of the oil by a syringe. After completion of the reaction, diethyl ether or CH2Cl2 (depending on the solubility of the substrate) was added to the reaction mixture and the organic layer was then extracted with 2N HCl or NH4Cl, and then with NaHCO3 or NH4OH. The aqueous layer was then washed once with ether or CH2Cl2. The organic layer was dried (Na2SO4), filtered, and concentrated to a viscous oil or solid. The residue was purified by preparative thin layer chromatography (silica, 0.5 mm thick plate) or Chromatotron"! (silica, 4 mm thick plate) to give the desired product, some being further recrystallized. 1-(Hex-1-ynyl)-2-methoxybenzene 8. Following the typical procedure, (hex-1-ynyl)methyl sulfide 1 (111 mg, 0.87 mmol, 1.0 equiv) was added to a mixture of CuTC (200 mg, 1.05 mmol, 1.2 equiv), 2-methoxyphenylboronic acid (146 mg, 0.96 mmol, 1.1 equiv) and Pd(PPh3)4 (47 mg, 0.04 mmol, 5%) in dry and degassed THF (5 mL). The reaction mixture was stirred for 14 h at 50 oC; 8 (111 mg, 0.59 mmol, 68 %) was obtained as a colorless oil after chromatography (Chromatotron"!, hexanes). TLC (hexanes-ether, 2:1, Rf = 0.55). IR (neat, KCl, cm-1): 2054 (w). 1H NMR (CDCl3, 400 MHz): 7.38 (dd, J = 7.6, 1.6 Hz, 1 H), 7.24 (dt, J = 8.4, 1.6 Hz, 1 H), 6.90-6.84 (m, 2 H), 3.87 (s, 3 H), 2.48 (t, J = 7.2 Hz, 2 H), 1.62 (pent, J = 7.2 Hz, 2 H), 1.51 (pent, J = 7.2 Hz, 2 H), 0.95 (t, J = 7.2 Hz, 3 H). 13C NMR (CDCl3, 100 MHz): 159.7, 133.6, 128.8, 120.3, 113.0, 110.4, 94.6, 76.5, 55.7, 30.9, 22.0, 19.4, 13.6. 3-E-1,4-Diphenyl-3-buten-1-yne 9. Following the typical procedure, dry and degassed THF (2.5 mL) was added to (phenylethynyl) (p-tolyl) sulfide 2 (99 mg, 0.44 mmol, 1.0 equiv), CuMeSal (103 mg, 0.48 mmol, 1.1 equiv), trans--styrylboronic acid (72 mg, 0.40 mmol, 1.1 equiv) and Pd(PPh3)4 (20 mg, 0.02 mmol, 4%). The reaction mixture was stirred for 14 h at 45 oC. After preparative plate chromatography (hexanes) and recrystallization from ethanol, 9 (61 mg, 0.30 mmol, 68 %) was obtained as a white solid. TLC (hexanes, Rf = 0.60). Mp 95-96 oC (ethanol; lit.{95-96 oC NOTEREF _Ref497451735 \f 9b}); IR (neat, cm-1): 1957 (w), 1887 (w). 1H NMR (CDCl3, 400 MHz): 7.42-7.49 (m, 4 H), 7.29-7.37 (m, 6 H), 7.05 (d, J = 16.4 Hz, 1 H), 6.39 (d, J = 16.4 Hz, 1 H). 5-Methyl-2-(phenylethynyl)thiophene 10. NOTEREF _Ref497451274 \f 10 Following the typical procedure, dry and degassed THF (3.5 mL) was added to (phenylethynyl) (p-tolyl) sulfide 2 (53 mg, 0.24 mmol, 1.0 equiv), CuTC (61.0 mg, 0.32 mmol, 1.3 equiv), 5-methylthiophene-2-boronic acid (45 mg, 0.32 mmol, 1.3 equiv), Pd(PPh3)4 (13 mg, 0.01 mmol, 5%). The reaction mixture was stirred for 15 h at room temperature. After preparative plate chromatography (hexanes) and recrystallization from methanol, 10 (41 mg, 0.21 mmol, 87 %) was obtained as a yellowish solid. TLC (hexanes, Rf = 0.37). Mp 56-57 oC (methanol; lit.{57-58 oC}); IR (CCl4, KCl, cm-1): 2208 (m), 1962 (w), 1941 (w), 1803 (w), 1747 (w). 1H NMR (CDCl3, 400): 7.51-7.48 (m, 2 H), 7.34-7.32 (m, 3 H), 7.08 (d, J = 3.6 Hz, 1 H), 6.66 (dd, J = 3.6, 0.8 Hz, 1 H), 2.49 (s, 3 H). [2,4-Bis(benzyloxy)pyrimidin-5-yl](phenyl)ethyne 11. Following the typical procedure, dry and degassed THF (3 mL) was added to (phenylethynyl) (p-tolyl) sulfide 2 (71 mg, 0.32 mmol, 1.0 equiv), CuMeSal (102 mg, 0.48 mmol, 1.5 equiv), 2,4-bis(benzyloxy)pyrimidinyl-5-boronic acid (166 mg, 0.49 mmol, 1.5 equiv) and Pd(PPh3)4 (24 mg, 0.02 mmol, 6%). The reaction mixture was stirred for 24 h at 45 oC. After preparative plate chromatography (CH2Cl2), 11 (49 mg, 0.12 mmol, 39 %) was obtained as a yellowish solid. TLC (hexanes: CH2Cl2, 1:1, Rf = 0.53). Mp 94-96 oC; IR (neat, cm-1): 2223 (w). 1H NMR (CDCl3, 400 MHz): 8.44 (s, 1 H), 7.51-7.46 (m, 6 H), 7.41-7.33 (m, 9 H), 5.52 (s, 2 H), 5.44 (s, 2 H). 13C NMR (CDCl3, 100 MHz): 169.9, 163.4, 161.3, 136.2, 135.9, 131.5, 128.5, 128.5, 128.3, 128.1, 128.1, 127.5, 122.9, 100.6, 95.7, 80.7, 69.6, 68.6; Anal. Calcd for C26H20O2N2: C, 79.57; H, 5.14; N, 7.14; O, 8.15; Found: C, 79.51; H, 5.31; N, 7.06; O, 7.91. 1-(3-Methoxyprop-1-ynyl)-3-nitrobenzene 12. Following the typical procedure, (3-methoxyprop-1-ynyl (p-tolyl) sulfide 3 (42 mg, 0.22 mmol, 1.0 equiv) was added to a mixture of CuTC (54 mg, 0.28 mmol, 1.3 equiv), 3-nitrophenylboronic acid (42 mg, 0.25 mmol, 1.1 equiv), and Pd(PPh3)4 (13 mg, 0.01 mmol, 4%) in dry and degassed THF (5 mL). The reaction mixture was stirred for 14 h at 45 oC. After preparative plate chromatography (hexanes-ether, 2:1), 12 (36 mg, 0.19 mmol, 86 %) was obtained as a colorless oil. TLC (hexanes-ether, 2:1, Rf = 0.50); IR (CCl4, KCl, cm-1): 2100 (w), 1782 (w), 1731 (w). 1H NMR (CDCl3, 400 MHz): 8.29 (t, J = 2.0 Hz, 1 H), 8.17 (ddd, J = 8.4, 2.4, 1.2 Hz, 1 H), 7.74 (td, J = 7.6, 1.2 Hz, 1 H), 7.50 (t, J = 8.0 Hz, 1 H), 4.34 (s, 2 H), 3.46 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 148.0, 137.3, 129.3, 126.6, 124.4, 123.2, 87.7, 83.9, 60.2, 57.9. Anal. Calcd for C10H9NO3 : C, 62.82; H, 4.74; N, 7.33; Found: C, 62.68; H, 4.73; N, 7.24. 3-(3,4-Methylenedioxyphenyl)propynoic acid ethyl ester 13.11 Following the typical procedure, 3-(p-tolylthio)propynoic acid ethyl ester 4 (28 mg, 0.13 mmol, 1.0 equiv) was added to a mixture of CuTC (31 mg, 0.16 mmol, 1.2 equiv), 3,4-methylenedioxyphenylboronic acid (26 mg, 0.16 mmol, 1.2 equiv) and Pd(PPh3)4 (8 mg, 0.01 mmol, 5%) in dry and degassed THF (3.5 mL). The reaction mixture was stirred for 14 h at 45 oC. After preparative plate chromatography (hexanes-ether, 2:1) and recrystallization from ether-hexanes, 13 (26 mg, 0.12 mmol, 91 %) was obtained as a white solid. TLC (hexanes-ether, 2:1, Rf = 0.60); Mp 79-80 oC (ether-hexanes; lit.{ethanol, 75-76 oC }); IR (CCl4, KCl, cm-1): 2213 (s), 1706 (s). 1H NMR (CDCl3, 400 MHz): 7.16 (dd, J = 8.0, 1.6 Hz, 1 H), 7.00 (d, J = 1.6 Hz, 1 H), 6.80 (d, J = 8.0 Hz, 1 H), 6.02 (s, 2 H), 4.28 (q, J = 7.2 Hz, 2 H), 1.35 (t, J = 7.2 Hz, 3 H). (p-Tolyl)[(3-trifluoromethylphenyl)ethynyl] sulfide 14. Following the typical procedure, dry and degassed THF (4 mL) was added to bis(p-tolylthio)ethyne 5 (89 mg, 0.33 mmol, 1.0 equiv), CuMeSal (88 mg, 0.41 mmol, 1.3 equiv), 3-trifluoromethylphenylboronic acid (62 mg, 0.33 mmol, 1.0 equiv) and Pd2(dba)3CHCl3 (9 mg, 0.01 mmol of Pd, 3% of Pd) and SbPh3 (26 mg, 0.07 mmol, 22%). The reaction mixture was stirred for 14 h at 45 oC. After preparative plate chromatography (hexanes) and recrystallization from ethanol, 14 (52 mg, 0.18 mmol, 54 %) was obtained as a white solid. TLC (hexanes, Rf = 0.46); Mp 59-60 oC (ethanol); IR (neat, cm-1): 2173 (m), 1494 (m). 1H NMR (CDCl3, 400 MHz): 7.73 (br s, 1 H), 7.64 (d, J = 7.6 Hz, 1 H), 7.57 (d, J = 8.0 Hz, 1 H), 7.46 (t, J = 7.6 Hz, 1 H), 7.38 (dt, J = 8.0, 2.0 Hz, 2 H), 7.19 (d, J = 8.0 Hz, 2 H), 2.35 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 137.1, 134.5, 130.2, 128.9, 128.4, 128.2 (q, J = 3.6 Hz), 127.0, 124.9 (q, J = 3.6 Hz), 123.9, 95.4, 78.7, 21.3 (the signals of the C of CF3 and in alpha of CF3 were not observed under the conditions of the experiment). 19F NMR (CDCl3, 376 MHz): - 64.3 (s). Anal. Calcd for C16H11SF3: C, 65.74; H, 3.79; S, 10.97; Found: C, 65.49; H, 3.89; S, 10.87. Bis(3-trifluoromethylphenyl)ethyne 15. NOTEREF _Ref497451400 \f 12 Following the typical procedure, dry and degassed THF (3 mL) was added to bis(p-tolylthio)ethyne 5 (34 mg, 0.13 mmol, 1.0 equiv), CuMeSal (92 mg, 0.43 mmol, 3.3 equiv), 3-trifluoromethylphenylboronic acid (77 mg, 0.41 mmol, 3.1 equiv), Pd(PPh3)4 (13 mg, 0.01 mmol, 10%). The reaction mixture was stirred for 14 h at 45 oC. After preparative plate chromatography (hexanes) and recrystallization from ethanol, 15 (30 mg, 0.10 mmol, 74 %) was obtained as a white solid. TLC (hexanes, Rf = 0.64); Mp 85-86 oC (ethanol; lit.{85-87 oC }); IR (neat, cm-1): 1729 (m). 1H NMR (CDCl3, 400 MHz): 7.81 (br s, 2 H), 7.71 (d, J = 7.6 Hz, 2 H), 7.61 (d, J = 7.6 Hz, 2 H), 7.50 (t, J = 7.6 Hz, 2 H). 19F NMR (CDCl3, 376 MHz): -64.3 (s). Bis(4-methoxyphenyl)ethyne 16. Following the typical procedure, dry and degassed THF (3 mL) was added to bis(p-tolylthio)ethyne 5 (53 mg, 0.20 mmol, 1.0 equiv), CuTC (87 mg, 0.46 mmol, 2.3 equiv), 4-methoxyphenylboronic acid (78 mg, 0.51 mmol, 2.6 equiv), Pd2(dba)3CHCl3 (5 mg, 0.01 mmol of Pd, 5% of Pd) and tris-2-furylphosphine (3 mg, 0.01 mmol, 6%). The reaction mixture was stirred for 12 h at 50 oC. After chromatography (Chromatotron"!, hexanes) and recrystallization from ethanol, 16 (30 mg, 0.13 mmol, 65 %) was obtained as a white solid. TLC (hexanes-ether, 2:1, Rf = 0.39); Mp 140-141 oC (ethanol; lit.{141-143 oC NOTEREF _Ref497451460 \f 13b}); 1H NMR (CDCl3, 400 MHz): 7.45 (td, J = 8.4, 2.8 Hz, 4 H), 6.87 (td, J = 8.4, 2.8 Hz, 4 H), 3.83 (s, 6 H). 1-[(Cyclohex-1-enyl)ethynyl]-4-methoxybenzene 17. Following the typical procedure, [2-(cyclohex-1-enyl)ethynyl] (p-tolyl) sulfide 6 (29 mg, 0.13 mmol, 1.0 equiv) was added to a mixture of CuTC (30 mg, 0.16 mmol, 1.2 equiv), 4-methoxyphenyl boronic acid (26 mg, 0.17 mmol, 1.3 equiv) and Pd(PPh3)4 (7 mg, 0.01 mmol, 5%) in dry and degassed THF (4 mL). The reaction mixture was stirred for 14 h at 50 oC. After preparative plate chromatography (hexanes) and recrystallization from ethanol, 17 (20 mg, 0.09 mmol, 74 %) was obtained as a white solid. TLC (hexanes, Rf = 0.15); Mp 52-53 oC (ethanol); IR (CCl4, KCl, cm-1): 2197 (m), 1731 (m). 1H NMR (CDCl3, 400 MHz): 7.36 (d, J = 8.8 Hz, 2 H), 6.83 (d, J = 8.8 Hz, 2 H), 6.17 (pent, J = 2.0 Hz, 1 H), 3.80 (s, 3 H), 2.22-2.19 (m, 2 H), 2.15-2.12 (m, 2 H), 1.70-1.59 (m, 4 H). 13C NMR (CDCl3, 100 MHz): 159.2, 134.5, 132.8, 120.8, 115.8, 113.8, 89.8, 86.6, 55.2, 29.3, 25.7, 22.3, 21.5. LRMS (EI), m/e (relative intensity) 212 (M+, 100), 184, 165, 115, 57. HRMS (EI) Calcd for C15H16O: 212.1201. Found: 212.1203 (M+, error - 0.8 ppm). Anal. Calcd for C15H16O: C, 84.87; H, 7.60; Found: C, 84.02; H, 7.58. 3-Methoxy-13-methyl-17-[(4-methoxyphenyl)ethynyl]-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-17-ol 18. Following the typical procedure, dry and degassed THF (2.5 mL) was added to 7 (50 mg, 0.11 mmol, 1.0 equiv), CuMeSal (26 mg, 0.12 mmol, 1.1 equiv), p-methoxyphenylboronic acid (20 mg, 0.13 mmol, 1.1 equiv) and Pd(PPh3)4 (7 mg, 0.01 mmol, 5%). The reaction mixture was stirred for 14 h at 45 oC. After preparative plate chromatography (CH2Cl2), 18 (37 mg, 0.09 mmol, 81 %) was obtained as white crystals. TLC (CH2Cl2, Rf = 0.30). Mp 59-60 oC (lit.{60-62 oC NOTEREF _Ref497451552 \f 14}); IR (neat, cm-1): 3466 (br m), 2290 (w), 1606 (s). 1H NMR (CDCl3, 400 MHz): 7.39 (td, J = 8.8, 2.8 Hz, 2 H), 7.23 (d, J = 8.8 Hz, 1 H), 6.84 (td, J = 8.8, 2.8 Hz, 2 H), 6.72 (dd, J = 8.8, 2.8 Hz, 1 H), 6.63 (d, J = 2.8 Hz, 1 H), 3.81 (s, 3 H), 3.78 (s, 3 H), 2.90-2.84 (m, 2 H), 2.46-1.30 (m, 14 H), 0.93 (s, 3 H). 13C NMR (CDCl3, 100 MHz): 159.5, 157.4, 138.0, 133.1, 132.6, 115.0, 113.9, 113.7, 111.5, 91.3, 85.8, 80.3, 55.3, 55.2, 49.7, 47.6, 43.6, 39.5, 39.0, 33.0, 29.8, 27.2, 26.5, 22.9, 12.9. LRMS (FAB), m/e (relative intensity) 424 ([M++H+Li], 31), 423 ([M++Li], 100), 405 (26), 378 (17), 377 (26), 313 (31), 301 (24), 294 (67). HRMS (FAB) Calcd for C28H32O3Li: 423.2511. Found: 423.2507 ([M++Li], error  1.1 ppm). []25D = -41.0 (c 0.24 in CH2Cl2). Control Experiments. Synthesis of Pd(PPh3)2(S-p-tolyl)(CCC6H5) (II) 19. (Phenylethynyl) (p-tolyl) sulfide 2 (101 mg, 0.45 mmol, 1.0 equiv) was mixed with Pd(PPh3)4 (502 mg, 0.43 mmol, 1.0 equiv) in dry and degassed benzene (11 mL) at room temperature in the dark under argon. After 10 h, pentane (60 mL), was added and an orange solid precipitated. After filtration of the solid, the palladium complex 19 (230 mg, 0.27 mmol, 63 %) was obtained as a light orange solid. The filtrate contained PPh3 but no (phenylethynyl)(p-tolyl)sulfide 2. Complex 19 decomposes if left in solution at room temperature. Mp 95-108 oC (decomp); IR (neat, cm-1): 2115 (m). 31P NMR (benzene, 162 MHz): 27.73 ppm. LRMS (FAB), m/e (relative intensity) 731 ([M+-(S-p-tolyl)], 10), 661 (2), 630 (2). HRMS (FAB) Calcd for C44H35P2Pd ([M+-(S-p-tolyl)]: 731.1249. Found: 731.1285 (error +5.0 ppm). Anal. Calcd for C51H42P2PdS: C, 71.62; H, 4.95; S, 3.75; Anal. Calcd for C51H42P2PdS.1/2 H2O: C, 70.87; H, 5.01; S, 3.71; Found: C, 70.61; H, 5.00; S, 3.55. Cross-coupling of (phenylethynyl) (p-tolyl) sulfide 2 and PhB(OH)2 with NaTC in the absence of Cu(I) Following the typical procedure, dry and degassed THF (1 mL) was added to (phenylethynyl) (p-tolyl) sulfide 2 (29 mg, 0.13 mmol, 1.0 equiv), NaTC (28 mg, 0.19 mmol, 1.4 equiv), phenylboronic acid (22 mg, 0.18 mmol, 1.4 equiv) and Pd(PPh3)4 (7 mg, 0.01 mmol, 7%). The reaction mixture was stirred for 24 h at 45 oC. No product was detected by GC/MS (octadecane (33 mg, 0.13 mmol) was used as internal standard). Cross-coupling of palladium complex 19 and PhB(OH)2 with CuMeSal(I). Following the typical procedure, dry and degassed THF (0.8 mL) was added to complex 19 (11 mg, 0.01 mmol, 1.0 equiv), CuMeSal (3 mg, 0.01 mmol, 1.1 equiv), and phenylboronic acid (3 mg, 0.02 mmol, 1.9 equiv). The reaction mixture was stirred for 24 h at 45 oC. Diphenylacetylene was detected by GC/MS [octadecane (3 mg, 0.01 mmol) was used as internal standard]. Cross-coupling of palladium complex 19 and PhB(OH)2 without Cu(I) cofactor. Following the typical procedure, dry and degassed THF (1 mL) was added to complex 19 (11 mg, 0.01 mmol, 1.0 equiv) and phenylboronic acid (3 mg, 0.02 mmol, 1.9 equiv). The reaction mixture was stirred for 24 h at 50 oC. No product was detected by GC/MS [octadecane (3 mg, 0.01 mmol) was used as internal standard]. Cross-coupling of palladium complex 19 and PhB(OH)2 without Cu(I) cofactor and with NaOAc as a base. Following the typical procedure, dry and degassed THF (1 mL) was added to complex 19 (10 mg, 0.01 mmol, 1.0 equiv), phenylboronic acid (3 mg, 0.02 mmol, 1.9 equiv) and NaOAc (6 mg, 0.07 mmol, 6.0 equiv). The reaction mixture was stirred for 24 h at 50 oC. No product was detected by GC/MS [octadecane (3 mg, 0.01 mmol) was used as internal standard].  (a) Zhang, S.; Zhang, D.; Liebeskind, L. S. J. Org. Chem. 1997, 62, 2312-2313.  Reaction of disulfide and trisulfide with N-chlorocarboxamide. Furukawa, M.; Fujino, Y.; Kojima, Y.; Ono, M.; Hayashi, S. Chem. Pharm. Bull. 1972, 26, 9, 2024-2028.  The preparation of N-(alkylthio)- and N-(arylthio)succinimide. Abe, Y.; Nakabayashi, T.; Tsurugi, J. Bull. Chem. Soc. Jap. 1973, 46, 1898-1899.  Chiral Ti catalyst in asymmetric cycloaddition. Narasaka, K.; Hayashi, Y.; Shimadzu, H.; Niihata, S. J. Am. Chem. Soc. 1992, 114, 23, 8869-8885.  (a) Nucleophilic substitution at an acetylenic carbon. Miller, S. I.; Orzech, C. E.; Welch, C. A.; Ziegler, G. R.; Dickstein, J. I. J. Am. Chem. Soc. 1962, 84, 2020-2021. (b) Kinetics and mechanism of the nucleophilic substitution of arylhalogeno acetylenes by sodium toluene-p-thiolate in N, N-dimethylformamide. Beltrame, P. L.; Cattania, M. G.; Simonetta, M. J. Chem. Soc. Perkin Trans 2 1973, 63-66.  Asymmetric approaches to cyclopentenones in the Ni(0)-promoted cyclocarbonylation reaction of allyl halides and acetylenes. Villar, J. M.; Degado, A.; Llebaria, A.; Moreto, J. M.; Molins, E.; Miravitlles, C. Tetrahedron 1996, 52, 31, 10525-10546.  Nucleophilic substitution at an acetylenic carbon: acetylenic thioethers from haloalkynes and sodium thiolates. Ziegler, G. R.; Welch, C. A.; Orzech, C. E.; Kikkawa, S.; Miller, S. I. J. Am. Chem. Soc. 1963, 85, 1648-1650.  A new synthesis of 2-substituted benzofurans and benzothiophens: novel fragmentation reactions of simple alkyl groups. Aitken, R. A.; Burns, G. Tetrahedron Lett. 1987, 28, 32, 3717-3718.  (a) Palladium-catalyzed coupling of organostannanes with hypervalent iodonium salts. Kang, S-H.; Lee, H-W.; Jang, S-B.; Kim, T-H.; Kim, J-S. Synth. Commun. 1996, 26, 23, 4311-4318. (b) Synthesis of (E)-1, 4-bis(organyl)but-1-en-3-ynes by lithium-tellurium exchange reaction on (Z)-1-butyltelluro-1,4-bis(organyl)but-1-en-3ynes. Dabdoub, M. J.; Dabdoub, V. B.; Comasseto, J. V. Tetrahedron Lett. 1992, 33, 17, 2261-2264.  Thiophene aus alkinen. Schulte, K. E.; Reisch, J.; Horner, L. Chem. Ber. 1962, 95, 1943-1952.  Synergists of insecticides IV. Polarography of some 4-substituted 1,2-(methylenedioxy)benzenes. Lurik, B. B.; Marinova, R. I.; Volkov, Y. P. J. Gen. Chem. USSR 1975, 2246-2249.  Oxidation of aromatic compounds VI. Oxidation of unsymmetrical diarylacetylenes in the CF3COOH-CH2Cl2-PbO2 system. Vasilev, A.V.; Rudenko, A.P Russ. J. Org. Chem. 1997, 33, 11, 1555-1584.  (a) Synthesis of aryl cluster glycosides by cyclotrimerization of 2-propynyl carbohydrate derivatives. Kaufman, R. J.; Sidhu, R. S. J. Org. Chem. 1982, 47, 25, 4941-4947. (b) Rudenko, A. P.; Vasilev, A. V. Russ. J. Org. Chem. 1995, 31, 10, 1360-1379.  The palladium-catalyzed reductive addition of aryl iodides to propargyl alcohols: a route to ,-diarylallylic alcohols. Arcadi, A.; Cacchi, S.; Marinelli, F.Tetrahedron 1985, 41, 22, 5121-5131. 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LiebeskindiC:\Manuscripts_Reports_Theses\Active Manuscripts\Savarin Alkyne Synthesis\Savarin Alkyne Experimental.docLanny S. LiebeskindiC:\Manuscripts_Reports_Theses\Active Manuscripts\Savarin Alkyne Synthesis\Savarin Alkyne Experimental.docLanny S. LiebeskindiC:\Manuscripts_Reports_Theses\Active Manuscripts\Savarin Alkyne Synthesis\Savarin Alkyne Experimental.docLanny S. LiebeskindiC:\Manuscripts_Reports_Theses\Active Manuscripts\Savarin Alkyne Synthesis\Savarin Alkyne Experimental.docLanny S. LiebeskindiC:\Manuscripts_Reports_Theses\Active Manuscripts\Savarin Alkyne Synthesis\Savarin Alkyne Experimental.docLanny S. LiebeskindiC:\Manuscripts_Reports_Theses\Active Manuscripts\Savarin Alkyne Synthesis\Savarin Alkyne Experimental.docLanny S. LiebeskindiC:\Manuscripts_Reports_Theses\Active Manuscripts\Savarin Alkyne Synthesis\Savarin Alkyne Experimental.docLanny S. LiebeskindiC:\Manuscripts_Reports_Theses\Active Manuscripts\Savarin Alkyne Synthesis\Savarin Alkyne Experimental.docLanny S. LiebeskindiC:\Manuscripts_Reports_Theses\Active Manuscripts\Savarin Alkyne Synthesis\Savarin Alkyne Experimental.docLanny S. LiebeskindC:\Documents and Settings\Lanny S. Liebeskind\Application Data\Microsoft\Word\AutoRecovery save of Savarin Alkyne Experimental.asd Rt6V(Df6i)d,S,tIx/KO<3z\nyC& wF z&XW? m  8>th @ @ ^@ `OJQJo(h ^`OJQJo(oh ^`OJQJo(h ^`OJQJo(h ^`OJQJo(oh PP^P`OJQJo(h   ^ `OJQJo(h ^`OJQJo(oh !!^!`OJQJo(p0p^p`0o(.  ^ `. L ^ `L.xx^x`.HH^H`.L^`L.^`.^`.L^`L.88^8`o(()^`. L ^ `L.  ^ `.xx^x`.HLH^H`L.^`.^`.L^`L. 0^`06CJo(()^`.L^`L.^`.X X ^X `.(#L(#^(#`L.%%^%`.((^(`.+L+^+`L.h pp^p`OJQJo(h @ @ ^@ `OJQJo(oh ^`OJQJo(h ^`OJQJo(h ^`OJQJo(oh ^`OJQJo(h PP^P`OJQJo(h   ^ `OJQJo(oh ^`OJQJo(^`o(()^`.pLp^p`L.@ @ ^@ `.^`.L^`L.^`.^`.PLP^P`L.h pp^p`OJQJo(h @ @ ^@ `OJQJo(oh ^`OJQJo(h ^`OJQJo(h ^`OJQJo(oh ^`OJQJo(h PP^P`OJQJo(h   ^ `OJQJo(oh ^`OJQJo(88^8`o(()^`. 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