Reacción #87498

Ecuación de reacción

Ethyl acetate

(1S,2S,3S,4R,5S)-2,3,4-tris-benzyloxy-5-[4-chloro-3-(4-ethoxy-benzyl)-phenyl]-1-fluoromethyl-6,8-dioxa-bicyclo[3.2.1]octane

(1S,2S,3S,4R,5S)-2,3,4-tris-benzyloxy-5-[4-chloro-3-(4-ethoxy-benzyl)-phenyl]-1-chloromethyl-6,8-dioxa-bicyclo[3.2.1]octane

formic acid

→

title compound

(1S,2S,3S,4R,5S)-5-[4-Chloro-3-(4-ethoxy-benzyl)-phenyl]-1-chloromethyl-6,8-dioxa-bicyclo[3.2.1]octane-2,3,4-triol

Disolventes

ethanol

tetrahydrofuran

Condiciones de reacción

Tratamiento posterior

1. 1
   Filtraciónthe mixture was filtered through a short pad of Celite®
2. 2
   Concentraciónconcentrated in vacuo
3. 3
   OtroThe crude material was purified by flash chromatography over silica gel using a 4 g redisep silica cartridge (
4. 4
   Lavadoeluting with a gradient of 50 to 100% ethyl acetate in heptane)

Procedimiento

To a suspension of a mixture of (1S,2S,3S,4R,5S)-2,3,4-tris-benzyloxy-5-[4-chloro-3-(4-ethoxy-benzyl)-phenyl]-1-fluoromethyl-6,8-dioxa-bicyclo[3.2.1]octane and (1S,2S,3S,4R,5S)-2,3,4-tris-benzyloxy-5-[4-chloro-3-(4-ethoxy-benzyl)-phenyl]-1-chloromethyl-6,8-dioxa-bicyclo[3.2.1]octane (50 mg, 0.07 mmol) and palladium black (50 mg, 0.38 mmol, Aldrich® high surface area) in ethanol (0.5 mL) and tetrahydrofuran (0.1 mL) was added formic acid (0.10 mL, 2.80 mmol) and the resulting mixture was stirred at room temperature for 1.5 hours. Ethyl acetate was added and the mixture was filtered through a short pad of Celite® and concentrated in vacuo. The crude material was purified by flash chromatography over silica gel using a 4 g redisep silica cartridge (eluting with a gradient of 50 to 100% ethyl acetate in heptane) to afford the title compound as a solid (8.6 mg; ˜80% pure, contaminated with some Example 8). (LCMS) 455.2 (M+H+: positive mode). 1H NMR (400 MHz, METHANOL-d4) delta ppm 7.40 (t, J=1.17 Hz, 1 H), 7.34 (s, 1 H), 7.34 (s, 1 H), 7.05-7.09 (m, 2 H), 6.76-6.80 (m, 2 H), 4.18 (d, J=7.61 Hz, 1 H), 4.01 (s, 2 H), 3.97 (q, J=7.03 Hz, 2 H), 3.90 (d, J=12.30 Hz, 1H), 3.83 (dd, J=8.20, 1.56 Hz, 1 H), 3.72 (d, J=12.30 Hz, 1 H), 3.60-3.65 (m, 2H), 3.50-3.54 (m, 1 H), 1.33 (t, J=7.03 Hz, 3 H).

Fuente