2-(4-bromophenyl)sulfonylacetonitrile

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Suspend (4-Bromobenzenesulfonyl)-acetonitrile (10.41 g, 40.02 mmol) in THF and cooled to 0° C., and add borane-dimethylsulfide complex (10 M, 12 mL, 120 mmol) to the suspension which is allowed to slowly warm to ambient temperature. The next day, quench the reaction with a slow addition of methanol until off-gassing ceases. Concentrate the reaction to dryness and add more methanol and bring to reflux for 3 hours. Concentrate the reaction to dryness, then dissolve in dichloromethane and extract with 1 N HCl (2×150 mL). Make the acidic aqueous extracts basic using 50% NaOH and Na2CO3. Treat the aqueous solution with dioxane (500 mL) and di-tertbutylcarbonate (10.91 g, 50.00 mmol) for 3 days. Dilute the reaction with dichloromethane, separate the layers and re-extract the aqueous with dichloromethane. Wash the organic extracts with aqueous saturated sodium chloride, dry over MgSO4, filter and concentrate to yield a crude oil. Chromatograph on silica utilizing (0→5→8%) ethyl acetate in dichloromethane to afford the title compound (4.20 g, 11.53 mmol). MS(ES), m/z 307/309 (M+1 minus t-butyl). add borane-dimethylsulfide complex (10 M, 12 mL, 120 mmol) to the suspension which to slowly warm to ambient temperature The next day, quench the reaction Concentrate the reaction to dryness to reflux for 3 hours Concentrate the reaction to dryness extract with 1 N HCl (2×150 mL) Dilute separate the layers re-extract the aqueous with dichloromethane Wash the organic extracts with aqueous saturated sodium chloride dry over MgSO4 filter concentrate to yield a crude oil