thiepan-4-one

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 4-thiepanone (900 mg, 6.9 mmol, 1.1 eq) in dry dichloromethane (30 mL) was added activated molecular sieves (4 Å, beads, spatula tip full) and the solution was cooled to 0° C. using an ice water bath. Trimethylsilyl trifluoromethanesulfonate (1.25 mL, 6.9 mmol, 1.1 eq) was added dropwise to the ketone solution, followed by the dropwise addition of ethyl 5-bromo-1H-indole-7-carboxylate (1.69 g, 6.3 mmol, 1 eq) as a solution in dichloromethane (10 mL). The reaction mixture was stirred at rt for 2 h, then warmed to 35° C. for 45 minutes. The deep red reaction mixture was cooled to 0° C. and triethylsilane (2 mL, 12.6 mmol, 2 eq) was added. The mixture was warmed to rt for 30 minutes, then was quenched by the addition of saturated aq. sodium bicarbonate. The aqueous layer was extracted with dichloromethane (2×50 mL), and the combined organic extracts were dried over sodium sulfate, filtered through a thin pad of silica gel (to remove baseline impurities), eluting with 50% ethyl acetate in hexanes, and concentrated to afford the crude product as a yellow residue. The crude material was purified by Isco Combiflash, eluting with 0-30% ethyl acetate in hexanes (120 gram column). The title compound was obtained as a yellow residue (540 mg, 24%). warmed to 35° C. for 45 minutes The deep red reaction mixture was cooled to 0° C. The mixture was warmed to rt for 30 minutes was quenched by the addition of saturated aq. sodium bicarbonate The aqueous layer was extracted with dichloromethane (2×50 mL) the combined organic extracts were dried over sodium sulfate filtered through a thin pad of silica gel (to remove baseline impurities) eluting with 50% ethyl acetate in hexanes concentrated to afford the crude product as a yellow residue The crude material was purified by Isco Combiflash eluting with 0-30% ethyl acetate in hexanes (120 gram column)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a flask under argon in an ice-bath, the 4-thiepanone (200 mg, 1.536 mmol) in 6 mL of dried CH2Cl2 was first dried w/4 A sieves and then transferred via a double needle tubing (cannula). TMS-OTf (278 uL, 1.536 mmol) was added dropwise and the reaction was stirred for 10 min. A solution of methyl 5-bromo-1H-indole-7-carboxylate (390 mg, 1.536 mmol) in 7 mL of CH2Cl2 was dried with 4 A sieves and then added into above solution dropwise. Stirring continued for 4 hours and the reaction was warmed to room temperature. The mixture was cooled to 0° C. and triethylsilane (245 uL, 1.536 mmol) was added as one portion. The mixture was stirred overnight then warmed to room temperature. The mixture was quenched water and sat. NaHCO3, then diluted water/AcOEt and washed with H2O and brine. 194 mg of crude product was obtained. added into above solution dropwise Stirring continued for 4 hours The mixture was cooled to 0° C. The mixture was stirred overnight then warmed to room temperature The mixture was quenched water and sat. NaHCO3 diluted water/AcOEt and washed with H2O and brine

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 4-thiepanone (900 mg, 6.9 mmol, 1.1 eq) in dry dichloromethane (30 mL) was added activated molecular sieves (4 Å, beads, spatula tip full) and the solution was cooled to 0° C. using an ice water bath. Trimethylsilyl trifluoromethanesulfonate (1.25 mL, 6.9 mmol, 1.1 eq) was added dropwise to the ketone solution, followed by the dropwise addition of ethyl 5-bromo-1H-indole-7-carboxylate (1.69 g, 6.3 mmol, 1 eq) as a solution in dichloromethane (10 mL). The reaction mixture was stirred at rt for 2 h, then warmed to 35° C. for 45 minutes. The deep red reaction mixture was cooled to 0° C. and triethylsilane (2 mL, 12.6 mmol, 2 eq) was added. The mixture was warmed to rt for 30 minutes, then was quenched by the addition of saturated aq. sodium bicarbonate. The aqueous layer was extracted with dichloromethane (2×50 mL), and the combined organic extracts were dried over sodium sulfate, filtered through a thin pad of silica gel (to remove baseline impurities), eluting with 50% ethyl acetate in hexanes, and concentrated to afford the crude product as a yellow residue. The crude material was purified by Isco Combiflash, eluting with 0-30% ethyl acetate in hexanes (120 gram column). The title compound was obtained as a yellow residue (540 mg, 24%). warmed to 35° C. for 45 minutes The deep red reaction mixture was cooled to 0° C. The mixture was warmed to rt for 30 minutes was quenched by the addition of saturated aq. sodium bicarbonate The aqueous layer was extracted with dichloromethane (2×50 mL) the combined organic extracts were dried over sodium sulfate filtered through a thin pad of silica gel (to remove baseline impurities) eluting with 50% ethyl acetate in hexanes concentrated to afford the crude product as a yellow residue The crude material was purified by Isco Combiflash eluting with 0-30% ethyl acetate in hexanes (120 gram column)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 4-thiepanone (900 mg, 6.9 mmol, 1.1 eq) in dry dichloromethane (30 mL) was added activated molecular sieves (4 Å, beads, spatula tip full) and the solution was cooled to 0° C. using an ice water bath. Trimethylsilyl trifluoromethanesulfonate (1.25 mL, 6.9 mmol, 1.1 eq) was added dropwise to the ketone solution, followed by the dropwise addition of ethyl 5-bromo-1H-indole-7-carboxylate (1.69 g, 6.3 mmol, 1 eq) as a solution in dichloromethane (10 mL). The reaction mixture was stirred at rt for 2 h, then warmed to 35° C. for 45 minutes. The deep red reaction mixture was cooled to 0° C. and triethylsilane (2 mL, 12.6 mmol, 2 eq) was added. The mixture was warmed to rt for 30 minutes, then was quenched by the addition of saturated aq. sodium bicarbonate. The aqueous layer was extracted with dichloromethane (2×50 mL), and the combined organic extracts were dried over sodium sulfate, filtered through a thin pad of silica gel (to remove baseline impurities), eluting with 50% ethyl acetate in hexanes, and concentrated to afford the crude product as a yellow residue. The crude material was purified by Isco Combiflash, eluting with 0-30% ethyl acetate in hexanes (120 gram column). The title compound was obtained as a yellow residue (540 mg, 24%). warmed to 35° C. for 45 minutes The deep red reaction mixture was cooled to 0° C. The mixture was warmed to rt for 30 minutes was quenched by the addition of saturated aq. sodium bicarbonate The aqueous layer was extracted with dichloromethane (2×50 mL) the combined organic extracts were dried over sodium sulfate filtered through a thin pad of silica gel (to remove baseline impurities) eluting with 50% ethyl acetate in hexanes concentrated to afford the crude product as a yellow residue The crude material was purified by Isco Combiflash eluting with 0-30% ethyl acetate in hexanes (120 gram column)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a flask under argon in an ice-bath, the 4-thiepanone (200 mg, 1.536 mmol) in 6 mL of dried CH2Cl2 was first dried w/4 A sieves and then transferred via a double needle tubing (cannula). TMS-OTf (278 uL, 1.536 mmol) was added dropwise and the reaction was stirred for 10 min. A solution of methyl 5-bromo-1H-indole-7-carboxylate (390 mg, 1.536 mmol) in 7 mL of CH2Cl2 was dried with 4 A sieves and then added into above solution dropwise. Stirring continued for 4 hours and the reaction was warmed to room temperature. The mixture was cooled to 0° C. and triethylsilane (245 uL, 1.536 mmol) was added as one portion. The mixture was stirred overnight then warmed to room temperature. The mixture was quenched water and sat. NaHCO3, then diluted water/AcOEt and washed with H2O and brine. 194 mg of crude product was obtained. added into above solution dropwise Stirring continued for 4 hours The mixture was cooled to 0° C. The mixture was stirred overnight then warmed to room temperature The mixture was quenched water and sat. NaHCO3 diluted water/AcOEt and washed with H2O and brine

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a flask under argon in an ice-bath, the 4-thiepanone (200 mg, 1.536 mmol) in 6 mL of dried CH2Cl2 was first dried w/4 A sieves and then transferred via a double needle tubing (cannula). TMS-OTf (278 uL, 1.536 mmol) was added dropwise and the reaction was stirred for 10 min. A solution of methyl 5-bromo-1H-indole-7-carboxylate (390 mg, 1.536 mmol) in 7 mL of CH2Cl2 was dried with 4 A sieves and then added into above solution dropwise. Stirring continued for 4 hours and the reaction was warmed to room temperature. The mixture was cooled to 0° C. and triethylsilane (245 uL, 1.536 mmol) was added as one portion. The mixture was stirred overnight then warmed to room temperature. The mixture was quenched water and sat. NaHCO3, then diluted water/AcOEt and washed with H2O and brine. 194 mg of crude product was obtained. added into above solution dropwise Stirring continued for 4 hours The mixture was cooled to 0° C. The mixture was stirred overnight then warmed to room temperature The mixture was quenched water and sat. NaHCO3 diluted water/AcOEt and washed with H2O and brine

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 4-thiepanone (900 mg, 6.9 mmol, 1.1 eq) in dry dichloromethane (30 mL) was added activated molecular sieves (4 Å, beads, spatula tip full) and the solution was cooled to 0° C. using an ice water bath. Trimethylsilyl trifluoromethanesulfonate (1.25 mL, 6.9 mmol, 1.1 eq) was added dropwise to the ketone solution, followed by the dropwise addition of ethyl 5-bromo-1H-indole-7-carboxylate (1.69 g, 6.3 mmol, 1 eq) as a solution in dichloromethane (10 mL). The reaction mixture was stirred at rt for 2 h, then warmed to 35° C. for 45 minutes. The deep red reaction mixture was cooled to 0° C. and triethylsilane (2 mL, 12.6 mmol, 2 eq) was added. The mixture was warmed to rt for 30 minutes, then was quenched by the addition of saturated aq. sodium bicarbonate. The aqueous layer was extracted with dichloromethane (2×50 mL), and the combined organic extracts were dried over sodium sulfate, filtered through a thin pad of silica gel (to remove baseline impurities), eluting with 50% ethyl acetate in hexanes, and concentrated to afford the crude product as a yellow residue. The crude material was purified by Isco Combiflash, eluting with 0-30% ethyl acetate in hexanes (120 gram column). The title compound was obtained as a yellow residue (540 mg, 24%). warmed to 35° C. for 45 minutes The deep red reaction mixture was cooled to 0° C. The mixture was warmed to rt for 30 minutes was quenched by the addition of saturated aq. sodium bicarbonate The aqueous layer was extracted with dichloromethane (2×50 mL) the combined organic extracts were dried over sodium sulfate filtered through a thin pad of silica gel (to remove baseline impurities) eluting with 50% ethyl acetate in hexanes concentrated to afford the crude product as a yellow residue The crude material was purified by Isco Combiflash eluting with 0-30% ethyl acetate in hexanes (120 gram column)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 4-thiepanone (900 mg, 6.9 mmol, 1.1 eq) in dry dichloromethane (30 mL) was added activated molecular sieves (4 Å, beads, spatula tip full) and the solution was cooled to 0° C. using an ice water bath. Trimethylsilyl trifluoromethanesulfonate (1.25 mL, 6.9 mmol, 1.1 eq) was added dropwise to the ketone solution, followed by the dropwise addition of ethyl 5-bromo-1H-indole-7-carboxylate (1.69 g, 6.3 mmol, 1 eq) as a solution in dichloromethane (10 mL). The reaction mixture was stirred at rt for 2 h, then warmed to 35° C. for 45 minutes. The deep red reaction mixture was cooled to 0° C. and triethylsilane (2 mL, 12.6 mmol, 2 eq) was added. The mixture was warmed to rt for 30 minutes, then was quenched by the addition of saturated aq. sodium bicarbonate. The aqueous layer was extracted with dichloromethane (2×50 mL), and the combined organic extracts were dried over sodium sulfate, filtered through a thin pad of silica gel (to remove baseline impurities), eluting with 50% ethyl acetate in hexanes, and concentrated to afford the crude product as a yellow residue. The crude material was purified by Isco Combiflash, eluting with 0-30% ethyl acetate in hexanes (120 gram column). The title compound was obtained as a yellow residue (540 mg, 24%). warmed to 35° C. for 45 minutes The deep red reaction mixture was cooled to 0° C. The mixture was warmed to rt for 30 minutes was quenched by the addition of saturated aq. sodium bicarbonate The aqueous layer was extracted with dichloromethane (2×50 mL) the combined organic extracts were dried over sodium sulfate filtered through a thin pad of silica gel (to remove baseline impurities) eluting with 50% ethyl acetate in hexanes concentrated to afford the crude product as a yellow residue The crude material was purified by Isco Combiflash eluting with 0-30% ethyl acetate in hexanes (120 gram column)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a flask under argon in an ice-bath, the 4-thiepanone (200 mg, 1.536 mmol) in 6 mL of dried CH2Cl2 was first dried w/4 A sieves and then transferred via a double needle tubing (cannula). TMS-OTf (278 uL, 1.536 mmol) was added dropwise and the reaction was stirred for 10 min. A solution of methyl 5-bromo-1H-indole-7-carboxylate (390 mg, 1.536 mmol) in 7 mL of CH2Cl2 was dried with 4 A sieves and then added into above solution dropwise. Stirring continued for 4 hours and the reaction was warmed to room temperature. The mixture was cooled to 0° C. and triethylsilane (245 uL, 1.536 mmol) was added as one portion. The mixture was stirred overnight then warmed to room temperature. The mixture was quenched water and sat. NaHCO3, then diluted water/AcOEt and washed with H2O and brine. 194 mg of crude product was obtained. added into above solution dropwise Stirring continued for 4 hours The mixture was cooled to 0° C. The mixture was stirred overnight then warmed to room temperature The mixture was quenched water and sat. NaHCO3 diluted water/AcOEt and washed with H2O and brine

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 4-thiepanone (900 mg, 6.9 mmol, 1.1 eq) in dry dichloromethane (30 mL) was added activated molecular sieves (4 Å, beads, spatula tip full) and the solution was cooled to 0° C. using an ice water bath. Trimethylsilyl trifluoromethanesulfonate (1.25 mL, 6.9 mmol, 1.1 eq) was added dropwise to the ketone solution, followed by the dropwise addition of ethyl 5-bromo-1H-indole-7-carboxylate (1.69 g, 6.3 mmol, 1 eq) as a solution in dichloromethane (10 mL). The reaction mixture was stirred at rt for 2 h, then warmed to 35° C. for 45 minutes. The deep red reaction mixture was cooled to 0° C. and triethylsilane (2 mL, 12.6 mmol, 2 eq) was added. The mixture was warmed to rt for 30 minutes, then was quenched by the addition of saturated aq. sodium bicarbonate. The aqueous layer was extracted with dichloromethane (2×50 mL), and the combined organic extracts were dried over sodium sulfate, filtered through a thin pad of silica gel (to remove baseline impurities), eluting with 50% ethyl acetate in hexanes, and concentrated to afford the crude product as a yellow residue. The crude material was purified by Isco Combiflash, eluting with 0-30% ethyl acetate in hexanes (120 gram column). The title compound was obtained as a yellow residue (540 mg, 24%). warmed to 35° C. for 45 minutes The deep red reaction mixture was cooled to 0° C. The mixture was warmed to rt for 30 minutes was quenched by the addition of saturated aq. sodium bicarbonate The aqueous layer was extracted with dichloromethane (2×50 mL) the combined organic extracts were dried over sodium sulfate filtered through a thin pad of silica gel (to remove baseline impurities) eluting with 50% ethyl acetate in hexanes concentrated to afford the crude product as a yellow residue The crude material was purified by Isco Combiflash eluting with 0-30% ethyl acetate in hexanes (120 gram column)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a flask under argon in an ice-bath, the 4-thiepanone (200 mg, 1.536 mmol) in 6 mL of dried CH2Cl2 was first dried w/4 A sieves and then transferred via a double needle tubing (cannula). TMS-OTf (278 uL, 1.536 mmol) was added dropwise and the reaction was stirred for 10 min. A solution of methyl 5-bromo-1H-indole-7-carboxylate (390 mg, 1.536 mmol) in 7 mL of CH2Cl2 was dried with 4 A sieves and then added into above solution dropwise. Stirring continued for 4 hours and the reaction was warmed to room temperature. The mixture was cooled to 0° C. and triethylsilane (245 uL, 1.536 mmol) was added as one portion. The mixture was stirred overnight then warmed to room temperature. The mixture was quenched water and sat. NaHCO3, then diluted water/AcOEt and washed with H2O and brine. 194 mg of crude product was obtained. added into above solution dropwise Stirring continued for 4 hours The mixture was cooled to 0° C. The mixture was stirred overnight then warmed to room temperature The mixture was quenched water and sat. NaHCO3 diluted water/AcOEt and washed with H2O and brine