2-trimethylsilylethanesulfonamide

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of tert-butyl 6′-bromo-1′-oxo-1′,3′-dihydrospiro[azetidine-3,2′-indene]-1-carboxylate (0.2863 g, 0.8 mmol), 2-(trimethylsilyl)ethanesulfonamide (0.2000 g, 1.1 mmol), and Ti(OEt)4 (0.6900 g, 3.0 mmol) in 1,2-dichloroethane (3 mL) was heated at 110° C. for 20 h. The reaction mixture was then quenched with ice, extracted with CH2Cl2, and dried over Na2SO4. After the solvent was evaporated under reduced pressure, the residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate to afford 0.4031 g (96%) of tert-butyl 6′-bromo-1′-(((2-(trimethylsilyl)ethyl)sulfonyl)imino)-1′,3′-dihydrospiro[azetidine-3,2′-indene]-1-carboxylate. LC-MS tR=2.31 min in 3 min chromatography, m/z 515, 517 (MH+), 459, 461 (MH+-56). The reaction mixture was then quenched with ice extracted with CH2Cl2 dried over Na2SO4 After the solvent was evaporated under reduced pressure the residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 6′-bromo-4-methoxyspiro[cyclohexane-1,2′-inden]-1′(3′H)-one (3) (0.9822 g, 3.18 mmol, 1.0 equiv) and 2-(trimethylsilyl)ethanesulfonamide) (SESNH2)(0.6338 g, 3.50 mmol, 1.1 equiv) in C1CH2CH2Cl (10 mL), cooled to 0° C., were successively added Et3N (0.9 mL, 6.46 mmol, 2.0 equiv) and TiCl4 (1.0 M in CH2Cl2, 3.4 mL, 3.4 mmol, 1.1 equiv). After 10 min, the ice bath was removed. The reaction mixture was stirred at room temperature for 3 h and then heated at 110° C. for 42 h. The reaction mixture was cooled to room temperature, quenched with water, and extracted with CH2Cl2. The combined organic phase was dried (Na2SO4) and evaporated. The residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate to afford 1.3685 g (91%) of N-(5′-bromo-4-methoxyspiro[cyclohexane-1,2′-indene]-3′(1′H)-ylidene)-2-(trimethylsilyl)ethanesulfonamide (8) as a solid. LC-MS tR=2.31 min in 3 min chromatography, m/z 472, 474 (MH+); 1H NMR (400 MHz, CDCl3) δ 8.78 (br s, 1H), 7.67 (dd, J=8.2, 1.8 Hz, 1H), 7.29 (d, J=8.2 Hz, 1H), 3.39 (s, 3H), 3.29-3.21 (m, 3H), 2.98 (s, 2H), 2.16-2.12 (m, 2H), 1.80-1.76 (m, 2H), 1.62-1.57 (m, 2H), 1.42-1.33 (m, 2H), 1.21-1.17 (m, 2H), 0.10 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 189.97, 151.30, 137.91, 133.35, 127.50, 121.43, 78.10, 55.80, 51.79, 51.39, 39.55, 33.97, 28.60, 9.98, −1.93. the ice bath was removed heated at 110° C. for 42 h The reaction mixture was cooled to room temperature quenched with water extracted with CH2Cl2 The combined organic phase was dried (Na2SO4) evaporated The residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 6′-bromo-4-methoxyspiro[cyclohexane-1,2′-inden]-1′(3′H)-one (3) (0.9822 g, 3.18 mmol, 1.0 equiv) and 2-(trimethylsilyl)ethanesulfonamide) (SESNH2)(0.6338 g, 3.50 mmol, 1.1 equiv) in C1CH2CH2Cl (10 mL), cooled to 0° C., were successively added Et3N (0.9 mL, 6.46 mmol, 2.0 equiv) and TiCl4 (1.0 M in CH2Cl2, 3.4 mL, 3.4 mmol, 1.1 equiv). After 10 min, the ice bath was removed. The reaction mixture was stirred at room temperature for 3 h and then heated at 110° C. for 42 h. The reaction mixture was cooled to room temperature, quenched with water, and extracted with CH2Cl2. The combined organic phase was dried (Na2SO4) and evaporated. The residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate to afford 1.3685 g (91%) of N-(5′-bromo-4-methoxyspiro[cyclohexane-1,2′-indene]-3′(1′H)-ylidene)-2-(trimethylsilyl)ethanesulfonamide (8) as a solid. LC-MS tR=2.31 min in 3 min chromatography, m/z 472, 474 (MH+); 1H NMR (400 MHz, CDCl3) δ 8.78 (br s, 1H), 7.67 (dd, J=8.2, 1.8 Hz, 1H), 7.29 (d, J=8.2 Hz, 1H), 3.39 (s, 3H), 3.29-3.21 (m, 3H), 2.98 (s, 2H), 2.16-2.12 (m, 2H), 1.80-1.76 (m, 2H), 1.62-1.57 (m, 2H), 1.42-1.33 (m, 2H), 1.21-1.17 (m, 2H), 0.10 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 189.97, 151.30, 137.91, 133.35, 127.50, 121.43, 78.10, 55.80, 51.79, 51.39, 39.55, 33.97, 28.60, 9.98, −1.93. the ice bath was removed heated at 110° C. for 42 h The reaction mixture was cooled to room temperature quenched with water extracted with CH2Cl2 The combined organic phase was dried (Na2SO4) evaporated The residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 3-formylpyridine (0.228 mL, 2.42 mmol) and 2-(trimethylsilyl)ethanesulfonamide (0.438 g, 2.42 mmol) in toluene (30 mL) was added boron trifluoride etherate (0.02 mL, 0.15 mmol) under Ar. The mixture was heated at reflux for 20 hours using a Dean-Stark trap. After cooling, 10% aqueous sodium bicarbonate was added, and the mixture was extracted with ethyl acetate. The combined organic extracts were washed with brine, dried (Na2SO4), filtered and concentrated to dryness to under reduced pressure obtain crude 2-trimethylsilyl-ethanesulfonic acid pyridin-3-ylmethyleneamide (669 mg), which was used directly in the next step. The mixture was heated at reflux for 20 hours After cooling the mixture was extracted with ethyl acetate The combined organic extracts were washed with brine dried (Na2SO4) filtered concentrated to dryness to under reduced pressure

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of tert-butyl 6′-bromo-1′-oxo-1′,3′-dihydrospiro[azetidine-3,2′-indene]-1-carboxylate (0.2863 g, 0.8 mmol), 2-(trimethylsilyl)ethanesulfonamide (0.2000 g, 1.1 mmol), and Ti(OEt)4 (0.6900 g, 3.0 mmol) in 1,2-dichloroethane (3 mL) was heated at 110° C. for 20 h. The reaction mixture was then quenched with ice, extracted with CH2Cl2, and dried over Na2SO4. After the solvent was evaporated under reduced pressure, the residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate to afford 0.4031 g (96%) of tert-butyl 6′-bromo-1′-(((2-(trimethylsilyl)ethyl)sulfonyl)imino)-1′,3′-dihydrospiro[azetidine-3,2′-indene]-1-carboxylate. LC-MS tR=2.31 min in 3 min chromatography, m/z 515, 517 (MH), 459, 461 (MH+-56). The reaction mixture was then quenched with ice extracted with CH2Cl2 dried over Na2SO4 After the solvent was evaporated under reduced pressure the residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 6′-bromo-4-methoxyspiro[cyclohexane-1,2′-inden]-1′(3′H)-one (3) (0.9822 g, 3.18 mmol, 1.0 equiv) and 2-(trimethylsilyl)ethanesulfonamide) (SESNH2) (0.6338 g, 3.50 mmol, 1.1 equiv) in ClCH2CH2Cl (10 mL), cooled to 0° C., were successively added Et3N (0.9 mL, 6.46 mmol, 2.0 equiv) and TiCl4 (1.0 M in CH2Cl2, 3.4 mL, 3.4 mmol, 1.1 equiv). After 10 min, the ice bath was removed. The reaction mixture was stirred at room temperature for 3 h and then heated at 110° C. for 42 h. The reaction mixture was cooled to room temperature, quenched with water, and extracted with CH2Cl2. The combined organic phase was dried (Na2SO4) and evaporated. The residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate to afford 1.3685 g (91%) of N-(5′-bromo-4-methoxyspiro[cyclohexane-1,2′-indene]-3′(1′H)-ylidene)-2-(trimethylsilyl)ethanesulfonamide (8) as a solid. LC-MS tR=2.31 min in 3 min chromatography, m/z 472, 474 (MH+); 1H NMR (400 MHz, CDCl3) δ 8.78 (br s, 1H), 7.67 (dd, J=8.2, 1.8 Hz, 1H), 7.29 (d, J=8.2 Hz, 1H), 3.39 (s, 3H), 3.29-3.21 (m, 3H), 2.98 (s, 2H), 2.16-2.12 (m, 2H), 1.80-1.76 (m, 2H), 1.62-1.57 (m, 2H), 1.42-1.33 (m, 2H), 1.21-1.17 (m, 2H), 0.10 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 189.97, 151.30, 137.91, 133.35, 127.50, 121.43, 78.10, 55.80, 51.79, 51.39, 39.55, 33.97, 28.60, 9.98, −1.93. the ice bath was removed heated at 110° C. for 42 h The reaction mixture was cooled to room temperature quenched with water extracted with CH2Cl2 The combined organic phase was dried (Na2SO4) evaporated The residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of tert-butyl 6′-bromo-1′-oxo-1′,3′-dihydrospiro[azetidine-3,2′-indene]-1-carboxylate (0.2863 g, 0.8 mmol), 2-(trimethylsilyl)ethanesulfonamide (0.2000 g, 1.1 mmol), and Ti(OEt)4 (0.6900 g, 3.0 mmol) in 1,2-dichloroethane (3 mL) was heated at 110° C. for 20 h. The reaction mixture was then quenched with ice, extracted with CH2Cl2, and dried over Na2SO4. After the solvent was evaporated under reduced pressure, the residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate to afford 0.4031 g (96%) of tert-butyl 6′-bromo-1′-(((2-(trimethylsilyl)ethyl)sulfonyl)imino)-1′,3′-dihydrospiro[azetidine-3,2′-indene]-1-carboxylate. LC-MS tR=2.31 min in 3 min chromatography, m/z 515, 517 (MH+), 459, 461 (MH+-56). The reaction mixture was then quenched with ice extracted with CH2Cl2 dried over Na2SO4 After the solvent was evaporated under reduced pressure the residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 6′-bromo-4-methoxyspiro[cyclohexane-1,2′-inden]-1′(3′H)-one (3) (0.9822 g, 3.18 mmol, 1.0 equiv) and 2-(trimethylsilyl)ethanesulfonamide) (SESNH2)(0.6338 g, 3.50 mmol, 1.1 equiv) in C1CH2CH2Cl (10 mL), cooled to 0° C., were successively added Et3N (0.9 mL, 6.46 mmol, 2.0 equiv) and TiCl4 (1.0 M in CH2Cl2, 3.4 mL, 3.4 mmol, 1.1 equiv). After 10 min, the ice bath was removed. The reaction mixture was stirred at room temperature for 3 h and then heated at 110° C. for 42 h. The reaction mixture was cooled to room temperature, quenched with water, and extracted with CH2Cl2. The combined organic phase was dried (Na2SO4) and evaporated. The residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate to afford 1.3685 g (91%) of N-(5′-bromo-4-methoxyspiro[cyclohexane-1,2′-indene]-3′(1′H)-ylidene)-2-(trimethylsilyl)ethanesulfonamide (8) as a solid. LC-MS tR=2.31 min in 3 min chromatography, m/z 472, 474 (MH+); 1H NMR (400 MHz, CDCl3) δ 8.78 (br s, 1H), 7.67 (dd, J=8.2, 1.8 Hz, 1H), 7.29 (d, J=8.2 Hz, 1H), 3.39 (s, 3H), 3.29-3.21 (m, 3H), 2.98 (s, 2H), 2.16-2.12 (m, 2H), 1.80-1.76 (m, 2H), 1.62-1.57 (m, 2H), 1.42-1.33 (m, 2H), 1.21-1.17 (m, 2H), 0.10 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 189.97, 151.30, 137.91, 133.35, 127.50, 121.43, 78.10, 55.80, 51.79, 51.39, 39.55, 33.97, 28.60, 9.98, −1.93. the ice bath was removed heated at 110° C. for 42 h The reaction mixture was cooled to room temperature quenched with water extracted with CH2Cl2 The combined organic phase was dried (Na2SO4) evaporated The residue was purified by chromatography on silica gel eluted with hexanes/ethyl acetate