Diazabicyclo(2.2.2)octane → 2,4,6-tri-O-benzyl-3-O-methyl-D-glucopyranose

HRID 583165

Reaction equation

HRID 583165 reaction equation
C([C:4]1([O:28][C@H:27]([CH2:29][O:30][CH2:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C@@H:18]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C@H:15]([O:16][CH3:17])[C@H:6]1[O:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[OH:5])C=C.N12CCC(CC1)CN2>C(O)C.C1C=CC=CC=1.O.CC(C)=O.O>[CH2:8]([O:7][C@@H:6]1[C@@H:15]([O:16][CH3:17])[C@H:18]([O:19][CH2:20][C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[C@@H:27]([CH2:29][O:30][CH2:31][C:32]2[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=2)[O:28][CH:4]1[OH:5])[C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1

Participants

5

Reactant 2

HCID 136165Diazabicyclo(2.2.2)octaneHCID 131720022allyl-3-O-methyl-2,4,6-tri-O-benzyl-glucopyranose

Product 1

HCID 541544682,4,6-tri-O-benzyl-3-O-methyl-D-glucopyranoseYield 73.4%

Reagents, catalysts & solvents 2

HCID 18366337Propan-2-one--water (1/1)SolventHCID 66847609Benzene ethanol waterSolvent

Procedure

Allyl-3-O-methyl-2,4,6-tri-O-benzyl-glucopyranose (7.4 g) was refluxed for 5 hours in a mixture of ethanol/benzene/water (7:3:1) (500 mL) containing tris triphenylphosphine rhodium (I) chloride (1.05 g) and diazabicyclo[2.2.2]octane (445 mg). The isomerized product was hydrolyzed in acetone-water (9:1) (140 mL) using mercuric chloride (18.6 g) and mercuric oxide (383 mg) by stirring the reaction mixture at room temperature for 1 hour. The resulting solution was evaporated to dryness, diluted with methylene chloride (500 mL), filtered and washed with 30% KBr (3×500 mL) and water (3×500 mL), dried over Na2SO4, concentrated and purified by chromatography on silica gel using hexane-ethyl acetate (4:1) and (3:1) as eluents to provide 2,4,6-tri-O-benzyl-3-O-methyl-D-glucopyranose (5.0 g).

Workup

  1. customThe resulting solution was evaporated to dryness
  2. additiondiluted with methylene chloride (500 mL)
  3. filtrationfiltered
  4. washwashed with 30% KBr (3×500 mL) and water (3×500 mL)
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. custompurified by chromatography on silica gel

Sources & evidence

ORD record
ord-d187fde7b6a848c18e36d85d12d5b830
Source dataset
uspto-grants-1999_07
Patent number
US05929037

Linked notes

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