Reacción #2722

ord-efe1cb2656924866b2ad6f8e5b445bf1

Ecuación de reacción

C[C@@H]1O[C@@H](O[C@@H]2[C@@H](OC(=O)c3ccccc3)[C@H](OCC[Si](C)(C)C)O[C@H](COC(=O)c3ccccc3)[C@H]2O[C@@H]2O[C@H](COC(=O)c3ccccc3)[C@H](O)[C@H](O)[C@H]2OC(=O)c2ccccc2)[C@@H](OCc2ccccc2)[C@H](OCc2ccccc2)[C@@H]1OCc1ccccc1
compound 10a
C[C@@H]1O[C@@H](O[C@@H]2[C@@H](OC(=O)c3ccccc3)[C@H](OCC[Si](C)(C)C)O[C@H](COC(=O)c3ccccc3)[C@H]2O[C@@H]2O[C@H](COC(=O)c3ccccc3)[C@H](O)[C@H](O)[C@H]2OC(=O)c2ccccc2)[C@@H](OCc2ccccc2)[C@H](OCc2ccccc2)[C@@H]1OCc1ccccc1
2-(Trimethylsilyl) ethyl 2,6-di-O-benzoyl-3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-4-O-(2,6-di-O-benzoyl-β-D-galactopyranosyl)-β-D-glucopyranoside
c1ccccc1
benzene
Cc1ccc(S(=O)(=O)O)cc1
4-toluenesulfonic acid
→
CC(=O)O[C@@H]1[C@H](O)[C@@H](OC(=O)c2ccccc2)[C@H](O[C@@H]2[C@H](O[C@@H]3O[C@@H](C)[C@@H](OCc4ccccc4)[C@@H](OCc4ccccc4)[C@@H]3OCc3ccccc3)[C@@H](OC(=O)c3ccccc3)[C@H](OCC[Si](C)(C)C)O[C@@H]2COC(=O)c2ccccc2)O[C@@H]1COC(=O)c1ccccc1
title compound 11a
Rendimiento 89.0%
CC(=O)O[C@@H]1[C@H](O)[C@@H](OC(=O)c2ccccc2)[C@H](O[C@@H]2[C@H](O[C@@H]3O[C@@H](C)[C@@H](OCc4ccccc4)[C@@H](OCc4ccccc4)[C@@H]3OCc3ccccc3)[C@@H](OC(=O)c3ccccc3)[C@H](OCC[Si](C)(C)C)O[C@@H]2COC(=O)c2ccccc2)O[C@@H]1COC(=O)c1ccccc1
2-(Trimethylsilyl) ethyl 2,6-di-O-benzoyl-4-O-(4-O-acetyl-2,6-di-O-benzoyl-β-D-galactopyranosyl)-3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-galactopyranoside
Rendimiento 89.0%

Reactantes

C[C@@H]1O[C@@H](O[C@@H]2[C@@H](OC(=O)c3ccccc3)[C@H](OCC[Si](C)(C)C)O[C@H](COC(=O)c3ccccc3)[C@H]2O[C@@H]2O[C@H](COC(=O)c3ccccc3)[C@H](O)[C@H](O)[C@H]2OC(=O)c2ccccc2)[C@@H](OCc2ccccc2)[C@H](OCc2ccccc2)[C@@H]1OCc1ccccc1
compound 10a
C[C@@H]1O[C@@H](O[C@@H]2[C@@H](OC(=O)c3ccccc3)[C@H](OCC[Si](C)(C)C)O[C@H](COC(=O)c3ccccc3)[C@H]2O[C@@H]2O[C@H](COC(=O)c3ccccc3)[C@H](O)[C@H](O)[C@H]2OC(=O)c2ccccc2)[C@@H](OCc2ccccc2)[C@H](OCc2ccccc2)[C@@H]1OCc1ccccc1
2-(Trimethylsilyl) ethyl 2,6-di-O-benzoyl-3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-4-O-(2,6-di-O-benzoyl-β-D-galactopyranosyl)-β-D-glucopyranoside
c1ccccc1
benzene
Cc1ccc(S(=O)(=O)O)cc1
4-toluenesulfonic acid

Reactivos

CCN(CC)CC
triethylamine

Disolventes

CCOC(C)(OCC)OCC
triethyl orthoacetate

Condiciones de reacción

Condiciones detalladas
See reaction.notes.procedure_details.

Tratamiento posterior

  1. 1
    Otrothe mixture evaporated to dryness
  2. 2
    workup.ADDITIONThe residue was mixed with 80% aqueous acetic acid (100 mL)
  3. 3
    workup.STIRRINGthe mixture stirred for 40 min at room temperature

Procedimiento

A solution of compound 10a (1.87 g), in a mixture of benzene (50 mL) and triethyl orthoacetate (50 mL), containing 4-toluenesulfonic acid (0.25 g) was stirred for 1 h at room temperature. The acid was then neutralized with a few drops of triethylamine, and the mixture evaporated to dryness. The residue was mixed with 80% aqueous acetic acid (100 mL) and the mixture stirred for 40 min at room temperature. Processing as described for 10b (to give 11b), gave the title compound 11a (1.86 g,89%); a white amorphous solid; [α]D -2.7° (c, 1.1, chloroform). 13C NMR (CDCl3): δ171.03 (CH3CO), 166.78, 166.35, 166.18, 165.02 (4×PhCO), 101.27, 101.09 (C-1, C-1'), 98.17 (C-1 fuc), 80.10, 78.20 (C-3, C-4), 74.67, 73.54, 73.30 (3×PhCH2), 67.86 (OCH2CH2Si), 63.31, 61.42 (C-6, C-6'), 21.21 (CH3 CO), 18.47 (OCH2CH2Si), and 17.53 (C-6 fuc); negative ion LSIMS: 1470.8 (M+mNBA)-, 1363.7 (M+NO2)-.

Fuente

DOI: 10.6084/m9.figshare.5104873.v1Patente: US05728685uspto-grants-1998_03