5-bromo-3,3-difluoro-1H-indol-2-one

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

実験手順: To a solution of 5-bromo-3,3-difluoroindolin-2-one (600 mg, 2.42 mmol) in DMF (5 mL), 60% NaH (69.6 mg, 2.90 mmol) was added. The resulting mixture was stirred at rt for 20 min and SEM-Cl (472 μL, 2.66 mmol) was added. The reaction mixture was stirred at rt overnight, poured into saturated NH4Cl (40 mL) and extracted with DCM (3×20 mL). The combined DCM layers were dried over Na2SO4, filtered, and concentrated. The residue obtained was purified by flash column chromatography on silica gel (0-100% EtOAc/hexanes) to obtain 5-bromo-3,3-difluoro-1-((2-(trimethylsilyl)ethoxy)methyl)indolin-2-one, which was subjected to borylation using the methods described in Example 32, Step B to obtain compound 37a. 1H-NMR (CDCl3, 400 MHz) δ (ppm): 8.33 (s, 1H), 8.04 (d, J=9.6 Hz, 1H), 7.57 (d, J=8.6 Hz, 1H), 5.46 (s, 2H), 3.75 (m, 2H), 1.27 (s, 12H), 0.95 (m, 2H). The reaction mixture was stirred at rt overnight extracted with DCM (3×20 mL) The combined DCM layers were dried over Na2SO4 filtered concentrated The residue obtained was purified by flash column chromatography on silica gel (0-100% EtOAc/hexanes)

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of 5-bromo-3,3-difluoroindolin-2-one (5.0 g, 20 mmol) in DMSO (50 mL), sodium methanesulfinate (3.0 g, 30 mmol), copper(I) trifluoromethane-sulfonate benzene complex (1.52 g, 3.022 mmol) and N,N′-dimethylethylenediamine (0.33 mL, 3.022 mmol) were added and stirred at 120° C. for 14 h. The reaction was quenched with water and the mixture was extracted with ethyl acetate. The organic layer was concentrated in vacuo and resulting residue was purified by flash column chromatography to give the title product (2.9 g, 58.2%); MS: 247.9 (M+1). The reaction was quenched with water the mixture was extracted with ethyl acetate The organic layer was concentrated in vacuo resulting residue was purified by flash column chromatography