methyl 5-bromo-2-methylsulfanylbenzoate

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

実験手順: To a THF (0.29 M) solution of 9-BBN (2 eq.) was added allyl methyl ether (2.1 eq.) dropwise and the resulting solution was stirred at RT until no more gaseous evolution was observed. The reaction mixture was then heated to 50° C. for 1 h. To this solution was subsequently added a DMF (0.34 M) solution of methyl 5-bromo-2-(methylthio)benzoate (1 eq.) from the previous step, potassium phosphate (2.5 eq.) and [1,1′-bis(diphenylphosphino)-ferrocene]dipalladium(II) dichloromethane complex (0.1 eq.). The resulting red suspension was heated at 80° C. for 16 h. After cooling to RT, the reaction was diluted with ether and water. The organic layer was separated and washed further with water and brine, dried over MgSO4, filtered and the filtrate concentrated in vacuo. Purification of the crude product thus obtained by way of flash chromatography (SiO2, 9:1 (v/v) Hex:EtOAc→7:3 (v/v) Hex:EtOAc) afforded the title compound as a colorless oil. The reaction mixture was then heated to 50° C. for 1 h The resulting red suspension was heated at 80° C. for 16 h After cooling to RT The organic layer was separated washed further with water and brine dried over MgSO4 filtered the filtrate concentrated in vacuo Purification of the crude product thus obtained by way of flash chromatography (SiO2, 9:1 (v/v) Hex:EtOAc→7:3 (v/v) Hex:EtOAc)

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

実験手順: To a DMF (0.2 M) suspension of cesium carbonate (3 eq.) and 5-bromo-2-mercaptobenzoic acid (1 eq.) was added iodomethane (5 eq.). The resulting suspension was then stirred at RT for 1 h. The volatiles were removed before EtOAc and sat. aq. NH4Cl were added. The organic phase was separated, dried over Na2SO4, filtered and the filtrate concentrated in vacuo to a pale yellow oil. This was taken up again in DMF (0.2 M) and added sequentially sodium hydride (3 eq.) and iodomethane (5 eq.). The reaction vessel was then sealed and heated to 70° C. for 16 h. After cooling to RT, EtOAc and sat. aq. NH4Cl were added to the crude reaction mixture. The organic phase was separated, dried over MgSO4, filtered and the filtrate concentrated in vacuo to a brown oil. Purification of the crude product thus obtained by way of flash chromatography (SiO2, Hex→3:2 (v/v) Hex:EtOAc) afforded the title compound as a light yellow solid. The volatiles were removed before EtOAc and sat. aq. NH4Cl were added The organic phase was separated dried over Na2SO4 filtered the filtrate concentrated in vacuo to a pale yellow oil The reaction vessel was then sealed heated to 70° C. for 16 h After cooling to RT reaction mixture The organic phase was separated dried over MgSO4 filtered the filtrate concentrated in vacuo to a brown oil Purification of the crude product thus obtained by way of flash chromatography (SiO2, Hex→3:2 (v/v) Hex:EtOAc)

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

実験手順: To a THF (0.29 M) solution of 9-BBN (2 eq.) was added allyl methyl ether (2.1 eq.) dropwise and the resulting solution was stirred at RT until no more gaseous evolution was observed. The reaction mixture was then heated to 50° C. for 1 h. To this solution was subsequently added a DMF (0.34 M) solution of methyl 5-bromo-2-(methylthio)benzoate (1 eq.) from the previous step, potassium phosphate (2.5 eq.) and [1,1′-bis(diphenylphosphino)-ferrocene]dipalladium(II) dichloromethane complex (0.1 eq.). The resulting red suspension was heated at 80° C. for 16 h. After cooling to RT, the reaction was diluted with ether and water. The organic layer was separated and washed further with water and brine, dried over MgSO4, filtered and the filtrate concentrated in vacuo. Purification of the crude product thus obtained by way of flash chromatography (SiO2, 9:1 (v/v) Hex:EtOAc→7:3 (v/v) Hex:EtOAc) afforded the title compound as a colorless oil. The reaction mixture was then heated to 50° C. for 1 h The resulting red suspension was heated at 80° C. for 16 h After cooling to RT The organic layer was separated washed further with water and brine dried over MgSO4 filtered the filtrate concentrated in vacuo Purification of the crude product thus obtained by way of flash chromatography (SiO2, 9:1 (v/v) Hex:EtOAc→7:3 (v/v) Hex:EtOAc)

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

実験手順: To a DMF (0.2 M) suspension of cesium carbonate (3 eq.) and 5-bromo-2-mercaptobenzoic acid (1 eq.) was added iodomethane (5 eq.). The resulting suspension was then stirred at RT for 1 h. The volatiles were removed before EtOAc and sat. aq. NH4Cl were added. The organic phase was separated, dried over Na2SO4, filtered and the filtrate concentrated in vacuo to a pale yellow oil. This was taken up again in DMF (0.2 M) and added sequentially sodium hydride (3 eq.) and iodomethane (5 eq.). The reaction vessel was then sealed and heated to 70° C. for 16 h. After cooling to RT, EtOAc and sat. aq. NH4Cl were added to the crude reaction mixture. The organic phase was separated, dried over MgSO4, filtered and the filtrate concentrated in vacuo to a brown oil. Purification of the crude product thus obtained by way of flash chromatography (SiO2, Hex→3:2 (v/v) Hex:EtOAc) afforded the title compound as a light yellow solid. The volatiles were removed before EtOAc and sat. aq. NH4Cl were added The organic phase was separated dried over Na2SO4 filtered the filtrate concentrated in vacuo to a pale yellow oil The reaction vessel was then sealed heated to 70° C. for 16 h After cooling to RT reaction mixture The organic phase was separated dried over MgSO4 filtered the filtrate concentrated in vacuo to a brown oil Purification of the crude product thus obtained by way of flash chromatography (SiO2, Hex→3:2 (v/v) Hex:EtOAc)

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

実験手順: To a THF (0.29 M) solution of 9-BBN (2 eq.) was added allyl methyl ether (2.1 eq.) dropwise and the resulting solution was stirred at RT until no more gaseous evolution was observed. The reaction mixture was then heated to 50° C. for 1 h. To this solution was subsequently added a DMF (0.34 M) solution of methyl 5-bromo-2-(methylthio)benzoate (1 eq.) from the previous step, potassium phosphate (2.5 eq.) and [1,1′-bis(diphenylphosphino)-ferrocene]dipalladium(II) dichloromethane complex (0.1 eq.). The resulting red suspension was heated at 80° C. for 16 h. After cooling to RT, the reaction was diluted with ether and water. The organic layer was separated and washed further with water and brine, dried over MgSO4, filtered and the filtrate concentrated in vacuo. Purification of the crude product thus obtained by way of flash chromatography (SiO2, 9:1 (v/v) Hex:EtOAc→7:3 (v/v) Hex:EtOAc) afforded the title compound as a colorless oil. The reaction mixture was then heated to 50° C. for 1 h The resulting red suspension was heated at 80° C. for 16 h After cooling to RT The organic layer was separated washed further with water and brine dried over MgSO4 filtered the filtrate concentrated in vacuo Purification of the crude product thus obtained by way of flash chromatography (SiO2, 9:1 (v/v) Hex:EtOAc→7:3 (v/v) Hex:EtOAc)

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

実験手順: To a DMF (0.2 M) suspension of cesium carbonate (3 eq.) and 5-bromo-2-mercaptobenzoic acid (1 eq.) was added iodomethane (5 eq.). The resulting suspension was then stirred at RT for 1 h. The volatiles were removed before EtOAc and sat. aq. NH4Cl were added. The organic phase was separated, dried over Na2SO4, filtered and the filtrate concentrated in vacuo to a pale yellow oil. This was taken up again in DMF (0.2 M) and added sequentially sodium hydride (3 eq.) and iodomethane (5 eq.). The reaction vessel was then sealed and heated to 70° C. for 16 h. After cooling to RT, EtOAc and sat. aq. NH4Cl were added to the crude reaction mixture. The organic phase was separated, dried over MgSO4, filtered and the filtrate concentrated in vacuo to a brown oil. Purification of the crude product thus obtained by way of flash chromatography (SiO2, Hex→3:2 (v/v) Hex:EtOAc) afforded the title compound as a light yellow solid. The volatiles were removed before EtOAc and sat. aq. NH4Cl were added The organic phase was separated dried over Na2SO4 filtered the filtrate concentrated in vacuo to a pale yellow oil The reaction vessel was then sealed heated to 70° C. for 16 h After cooling to RT reaction mixture The organic phase was separated dried over MgSO4 filtered the filtrate concentrated in vacuo to a brown oil Purification of the crude product thus obtained by way of flash chromatography (SiO2, Hex→3:2 (v/v) Hex:EtOAc)