(1S)-5-bromo-2,3-dihydro-1H-inden-1-ol

反応条件: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of (S)-5-bromo-indan-1-ol (15.0 g, 70.4 mmol) in toluene (150 mL) was cooled in an ice bath under N2 and was treated with diphenylphosphoric azide (DPPA, 22.0 g, 91.5 mmol) in one portion followed by 1,8-diazabicyclo[5,4,0]undec-7-ene (15.0 g, 98.6 mmol). The reaction temperature was kept between 3 and 10° C. during 3 hours of addition and the mixture was warmed to 15° C. over the next hour (TLC indicated no starting material). The mixture was diluted with EtOAc (300 mL) and was washed with water. The organic layer was dried over Na2SO4, filtered and concentrated to give a dark oil. The crude product was purified by silica gel column (packed with 1% Et3N in hexanes, hexane eluant) to give (R)-1-azido-5-bromo-indane (14 g, 83%) as an oil which was used directly in the next step. The reaction temperature was kept between 3 and 10° C. during 3 hours of addition was washed with water The organic layer was dried over Na2SO4 filtered concentrated to give a dark oil The crude product was purified by silica gel column (packed with 1% Et3N in hexanes, hexane eluant)

反応条件: temp:35.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A round-bottomed flask was charged with 5-bromo-1-indanone (50.0 g, 0.24 mol), anhydrous THF (500 mL) and (R)-methyl-CBS-oxazaborolidine (10.0 g, 0.04 mol) and the solution was heated to 35° C. under N2. Borane-methylsulfide (10.0 M, 650 mL, 6.5 mol) was added dropwise over 1.5 hours. The mixture was stirred at 35° C. for 1 hour. Upon consumption of the starting material (TLC analysis), the reaction was cooled to 0° C. and was quenched with water (200 mL) at such a rate to maintain the reaction temperature below 5° C. The mixture was extracted with EtOAc (4×200 mL). The combined organic extracts were washed with brine, dried over MgSO4, filtered and concentrated to give a yellow solid. The solids were dissolved in hot CHCl3 (150 mL) and hexane (300 mL) and upon cooling to room temperature solids precipitated from the solution. After further cooling at 0° C., the solids were collected by vacuum filtration to afford (S)-5-bromo-indan-1-ol (22 g, 44%) as a light-yellow solid. This material was carried on to the next step without further purification. Upon consumption of the starting material (TLC analysis) the reaction was cooled to 0° C. was quenched with water (200 mL) at such a rate to maintain the reaction temperature below 5° C The mixture was extracted with EtOAc (4×200 mL) The combined organic extracts were washed with brine dried over MgSO4 filtered concentrated to give a yellow solid precipitated from the solution After further cooling at 0° C. the solids were collected by vacuum filtration