1,4-Dibromobenzene → 2,3,4,6-tetra-O-benzyl-1-C-[2-(benzyloxy)-5-[(4-bromophenyl)(hydroxy)methyl]-4-methylphenyl]-D-glucopyranose

HRID 1009863Notes

Reaction equation

HRID 1009863 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][CH:3]=1.C([Li])CCC.CCCCCC.[CH2:20]([O:27][C@@H:28]1[C@@H:34]([O:35][CH2:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[C@H:33]([O:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[C@@H:32]([CH2:51][O:52][CH2:53][C:54]2[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=2)[O:31][C:29]1([C:60]1[CH:65]=[C:64]([CH:66]=[O:67])[C:63]([CH3:68])=[CH:62][C:61]=1[O:69][CH2:70][C:71]1[CH:76]=[CH:75][CH:74]=[CH:73][CH:72]=1)[OH:30])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.[Cl-].[NH4+]>O1CCCC1>[CH2:20]([O:27][C@@H:28]1[C@@H:34]([O:35][CH2:36][C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)[C@H:33]([O:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[C@@H:32]([CH2:51][O:52][CH2:53][C:54]2[CH:55]=[CH:56][CH:57]=[CH:58][CH:59]=2)[O:31][C:29]1([C:60]1[CH:65]=[C:64]([CH:66]([C:2]2[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][CH:3]=2)[OH:67])[C:63]([CH3:68])=[CH:62][C:61]=1[O:69][CH2:70][C:71]1[CH:72]=[CH:73][CH:74]=[CH:75][CH:76]=1)[OH:30])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

7

Reactant 5

HCID 78041,4-DibromobenzeneHCID 8058HexaneHCID 25517Ammonium ChlorideHCID 86638438HCID 86638438, compoundHCID 178418339Butyllithium

Product 1

HCID 866384392,3,4,6-tetra-O-benzyl-1-C-[2-(benzyloxy)-5-[(4-bromophenyl)(hydroxy)methyl]-4-methylphenyl]-D-glucopyranoseYield 46%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a tetrahydrofuran solution (80 mL) of 1,4-dibromobenzene (6.20 g, 26.1 mmol) was added dropwise under nitrogen atmosphere at −78° C. a 2.67 M n-butyllithium solution in hexane (10.5 mL, 26.1 mmol), and the mixture was stirred for 15 minutes at the same temperature. Then a tetrahydrofuran solution (20 mL) of 2,3,4,6-tetra-O-benzyl-1-C-[2-(benzyloxy)-5-formyl-4-methylphenyl]-D-glucopyranose (10.0 g, 13.0 mmol) was added dropwise, and the mixture was stirred for 30 minutes at the same temperature. To the reaction solution was added a saturated aqueous solution of ammonium chloride, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed with brine, and dried with anhydrous magnesium sulfate. The drying agent was filtered off, and the solvent was evaporated under reduced pressure. Thus obtained residue was purified with silica gel column chromatography (hexane:ethyl acetate=2:1). In addition, the residue was further purified with NH type silica gel column chromatography (hexane:ethyl acetate=1:1) to obtain the yellow oily title compound (5.50 g, 46%) as a diastereomeric mixture.

Workup

  1. stirringthe mixture was stirred for 30 minutes at the same temperature
  2. extractionthe resulting mixture was extracted with ethyl acetate
  3. washThe organic layer was washed with brine
  4. dry with materialdried with anhydrous magnesium sulfate
  5. filtrationThe drying agent was filtered off
  6. customthe solvent was evaporated under reduced pressure
  7. customThus obtained residue was purified with silica gel column chromatography (hexane:ethyl acetate=2:1)
  8. customIn addition, the residue was further purified with NH type silica gel column chromatography (hexane:ethyl acetate=1:1)

Sources & evidence

ORD record
ord-218af9e8803e40fabee6485f1927bbc4
Source dataset
uspto-grants-2011_07
Patent number
US07973012B2

Reaction notes

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