Dimethyl Sulfoxide → HCID 86722345, compound

Participants

Reaction Conditions

Reaction Steps

A mixture of DMSO (1 mL) and sodium hydride (60 wt % in oil, 0.020 g, 0.51 mmol) was heated to about 65° C. for about 45 min then cooled to rt and diluted with THF (1 mL). The mixture was cooled to about 0° C. and trimethylsulfoxonium iodide (0.112 g, 0.509 mmol) was added. The mixture was stirred for about 15 min and (4aS,12bR)-9-acetyl-12b-ethyl-1,2,4a,5,6,7,9,12b-octahydro-4H-9,10-diaza-benzo[3,4]cyclohepta[1,2-f]inden-3-one; compound with (4aR,12bS)-9-Acetyl-12b-ethyl-1,2,4a,5,6,7,9,12b-octahydro-4H-9,10-diaza-benzo[3,4]cyclohepta[1,2-f]inden-3-one (10, R1=Acetyl, R2=Ethyl) (0.066 g, 0.203 mmol) dissolved in THF (1.5 mL) was added. The mixture was warmed to rt and stirred for about 14 h. In a separate flask a mixture of DMSO (1 mL) and sodium hydride (60 wt % in oil, 0.020 g, 0.51 mmol) was heated to about 65° C. for about 45 min then cooled to rt and diluted with THF (0.5 mL). The mixture was cooled to about 0° C., trimethylsulfoxonium iodide (0.112 g, 0.51 mmol) was added and the mixture was stirred for about 15 min. The mixture was added to the epoxidation reaction and stirring was continued for about 2 h at rt. The reaction mixture was diluted with EtOAc (25 mL) and washed successively with sat. aq. NH4Cl (15 mL), water (15 mL), and brine (15 mL). The organic solution was died over MgSO4, filtered and concentrated under reduced pressure to provide crude rac-(2′R,4aS,12bR)-12b-ethyl-2,4,4a,5,6,7,9,12b-octahydro-1H-spiro[benzo[6,7]cyclohepta[1,2-f]indazole-3,2′-oxirane] (12, R1═H, R2=Ethyl) (0.084 g); LC/MS, method 3, Rt=2.32 min, MS m/z 297 (M+H)+. The material was used directly in Step #13 without further purification

Provenance & Evidence