Benzyl Bromide → Methyl 6-O-tert-butyldiphenylsilyl-2,3,4-tri-O-benzyl-beta-D-glucopyranoside

HRID 742114Notes

Reaction equation

HRID 742114 reaction equation
[H-].[Na+].[Si:3]([O:20][CH2:21][C@H:22]1[O:29][C@@H:26]([O:27][CH3:28])[C@H:25]([OH:30])[C@@H:24]([OH:31])[C@@H:23]1[OH:32])([C:16]([CH3:19])([CH3:18])[CH3:17])([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[CH2:33](Br)[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1>C1COCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[Si:3]([O:20][CH2:21][C@H:22]1[O:29][C@@H:26]([O:27][CH3:28])[C@H:25]([O:30][CH2:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C@@H:24]([O:31][CH2:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C@@H:23]1[O:32][CH2:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)([C:16]([CH3:17])([CH3:18])[CH3:19])([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

6

Reactant 3

HCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 11761839methyl 6-O-tert-butyldiphenylsilyl-beta-D-glucopyranoside

Product 1

HCID 11146901Methyl 6-O-tert-butyldiphenylsilyl-2,3,4-tri-O-benzyl-beta-D-glucopyranosideYield 69%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred suspension of sodium hydride (1.67 g, 41.6 mmol) in 100 mL of dry THF was added at 0° C. a solution of methyl 6-O-tert-butyldiphenylsilyl-β-D-glucopyranoside (4.0 g, 9.25 mmol) in 50 mL of dry THF. After 5 minutes, the suspension was warmed to room temperature and stirred for 1 hour. Benzyl bromide (5.50 mL, 46.2 mmol) was added at room temperature followed by tetrabutylammonium iodide (341 mg, 0.93 mmol). The suspension was warmed to 50° C. and stirred for 4 days. After quenching with 40 mL of saturated aqueous ammonium chloride, the resulting mixture was diluted with ether (600 mL) and washed with H2O (2×200 mL), saturated aqueous NaCl (1×200 mL), and dried over magnesium sulfate. Concentration and flash chromatography (silica, 10% ether in petroleum ether) provided pure target compound (4.48 g, 69%) as a clear oil.

Workup

  1. temperatureThe suspension was warmed to 50° C.
  2. stirringstirred for 4 days
  3. customAfter quenching with 40 mL of saturated aqueous ammonium chloride
  4. additionthe resulting mixture was diluted with ether (600 mL)
  5. washwashed with H2O (2×200 mL), saturated aqueous NaCl (1×200 mL)
  6. dry with materialdried over magnesium sulfate
  7. concentrationConcentration and flash chromatography (silica, 10% ether in petroleum ether)

Sources & evidence

ORD record
ord-4dc97c7f92a547388d12997126ea53bc
Source dataset
uspto-grants-1996_09
Patent number
US05552534

Reaction notes

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