triphenyl(sulfanyl)silane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask was charged with triphenylsilanethiol (12 g, 41 mmol), and 1,5-difluoro-2-nitro-4-vinylbenzene (5 g, 27 mmol) in benzene (80 mL), and then (E)-2,2′-(diazene-1,2-diyl)bis(2-methylpropanenitrile) (1.3 g, 8.1 mmol) was added. The mixture was refluxed for 1 hour, then cooled to ambient temperature and concentrated. The residue was purified using silica gel column chromatography with 10% acetone in hexanes to provide (2,4-difluoro-5-nitrophenethylthio)triphenylsilane (13 g, 27 mmol, 100% yield). The mixture was refluxed for 1 hour concentrated The residue was purified

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask was charged with triphenylsilanethiol (12 g, 41 mmol), and 1,5-difluoro-2-nitro-4-vinylbenzene (5 g, 27 mmol) in benzene (80 mL), and then (E)-2,2′-(diazene-1,2-diyl)bis(2-methylpropanenitrile) (1.3 g, 8.1 mmol) was added. The mixture was refluxed for 1 hour, then cooled to ambient temperature and concentrated. The residue was purified using silica gel column chromatography with 10% acetone in hexanes to provide (2,4-difluoro-5-nitrophenethylthio)triphenylsilane (13 g, 27 mmol, 100% yield). The mixture was refluxed for 1 hour concentrated The residue was purified

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl 2-ethyl-4-methylenecyclopentanecarboxylate (0.720 g, 3.95 mmol), triphenylsilanethiol (1.329 g, 4.54 mmol) and 2,2′-azobis(2-methylpropionitrile) (0.195 g, 1.185 mmol) in toluene (3.95 mL) was heated at reflux for about 6 h. The reaction mixture was cooled to ambient temperature and then concd under reduced pressure. The material was purified by silica gel (40 g) chromatography eluting with a gradient of 0-10% EtOAc in heptane to give a colorless oil. The resulting oil was dissolved in DCM (4 mL) and TFA (1.52 mL, 19.7 mmol) was added. After stirring at ambient temperature for about 1 h, the solvent was removed under reduced pressure. The material was purified by silica gel (40 g) chromatography eluting with a gradient of 0-15% EtOAc in heptane to provide ethyl 2-ethyl-4-(mercaptomethyl)cyclopentanecarboxylate (0.620 g, 72%) as a colorless oil: 1H NMR (DMSO-d6) δ 4.13-4.01 (m, 2H), 2.50-2.30 (m, 3H), 2.24 (m, 1H), 2.15-1.87 (m, 3H), 1.66-1.54 (m, 1H), 1.50-1.37 (m, 2H), 1.31-1.23 (m, 2H), 1.17 (t, 3H), 0.83 (m, 3H). at reflux for about 6 h The material was purified by silica gel (40 g) chromatography eluting with a gradient of 0-10% EtOAc in heptane to give a colorless oil the solvent was removed under reduced pressure The material was purified by silica gel (40 g) chromatography eluting with a gradient of 0-15% EtOAc in heptane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 3,N,N-trimethyl-4-vinyl-benzamide (706 mg, 3.73 mmol), triphenylsilanethiol (1.76 g, 6.00 mmol) and AIBN (185 mg, 1.13 mmol) in toluene (16 ml) was heated with stirring at 88° C. for two hours in a sealed test tube in an N2 atmosphere. The reaction mixture was cooled to room temperature and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate=2/1) to give 3,N,N-trimethyl-4-(2-triphenylsilanylsulfanyl-ethyl)-benzamide (1.24 g, 69%). was heated concentrated under reduced pressure The resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate=2/1)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of tert-butyl 1-oxa-6-azaspiro[2.5]octane-6-carboxylate (35.3 g, 16.55 mmol) and triphenylsilanethiol (48.4 g, 16.55 mmol) in anhydrous methanol (1.0 L) was added triethylamine (23.1 ml, 16.55 mmol) drop-wise over the course of 30 minutes. The reaction was stirred for 1 hour at room temperature and the methanol was evaporated under reduced pressure. The crude product was purified by flash column chromatography (SiO2, 5% EtOAc in hexanes to 40% EtOAc in hexanes) to afford 81% (33.1 g) pure final product. M.p.=54-55° C.; 400 MHz 1H NMR (CDCl3) δ: 3.97-3.78 (m, 2H), 3.19-3.08 (m, 2H), 2.61 (d, J=4.4 Hz, 2H), 1.70-1.55 (m, 2H), 1.50-1.38 (m, 11H); LCMS: 248 [M+H]. the methanol was evaporated under reduced pressure The crude product was purified by flash column chromatography (SiO2, 5% EtOAc in hexanes to 40% EtOAc in hexanes)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask was charged with triphenylsilanethiol (12 g, 41 mmol), and 1,5-difluoro-2-nitro-4-vinylbenzene (5 g, 27 mmol) in benzene (80 mL), and then (E)-2,2′-(diazene-1,2-diyl)bis(2-methylpropanenitrile) (1.3 g, 8.1 mmol) was added. The mixture was refluxed for 1 hour, then cooled to ambient temperature and concentrated. The residue was purified using silica gel column chromatography with 10% acetone in hexanes to provide (2,4-difluoro-5-nitrophenethylthio)triphenylsilane (13 g, 27 mmol, 100% yield). The mixture was refluxed for 1 hour concentrated The residue was purified