Benzoic Acid → D-Glucitol, 1,4:3,6-dianhydro-5-O-[(1,1-dimethylethyl)dimethylsilyl]-

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Reaction Steps

To a stirred solution of triphenylphosphine (542 mg, 2.066 mmol), benzoic acid (252 mg, 2.066 mmol), and (3R,3aR,6R,6aS)-6-((tert-butyldimethylsilyl)oxy)hexahydrofuro[3,2-b]furan-3-ol (538 mg, 2.066 mmol) in anhydrous THF (8.0 mL) under nitrogen at room temperature was added DIAD (0.40 mL, 418 mg, 2.066 mmol), dropwise, over 10 min. After stirring for 16 h at room temperature, the mixture was concentrated under reduced pressure. The resultant residue was chromatographed using a Biotage™ 50 g (2×25 g in series) silica gel cartridge eluting with 0-50% EtOAc in 1:1 Hexane/DCM over 20 column volumes. The fractions containing desired product were combined and concentrated under reduced pressure. The resultant colorless oil was dissolved in MeOH (10 mL), and 5N aqueous NaOH (2.0 mL, 10.0 mmol) was added. After stirring for 20 h at room temperature, the mixture was poured into saturated aqueous sodium bicarbonate (100 mL) and extracted with ethyl acetate (2×100 mL). The combined organic layers were dried over sodium sulfate, and then concentrated under reduced pressure to afford the title compound as a white solid. LC-MS: calculated for C12H24O4Si 260.14, observed m/e: 261.17 (M+H)+ (Rt 0.42/4 min)1H NMR (500 MHz, CDCl3): δ 4.49 (t, J=4.5 Hz, 1H), 4.34 (d, J=4.3 Hz, 1H), 4.25 (m, 2H), 3.92 (dd, J=10.0, 3.5 Hz, 1H), 3.84 (d, J=10.0 Hz, 1H), 3.73 (dd, J=8.5, 6.0 Hz, 1H), 3.50 (t, J=8.0 Hz, 1H), 2.84 (s, 1H), 0.88 (s, 9H), 0.09 (s, 3H), 0.08 (s, 3H).

Provenance & Evidence