Citric Acid → 4-{[Bis(benzyloxy)phosphoryl]oxy}-3,3-dimethylbutanoic acid

HRID 1968911Notes

Reaction equation

HRID 1968911 reaction equation
[P:1]([O:19][CH2:20][C:21]([CH3:26])([CH3:25])[CH2:22][CH2:23][OH:24])([O:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)([O:3][CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:2].[Cr](O[Cr]([O-])(=O)=O)([O-])(=O)=[O:28].[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>CN(C=O)C>[CH2:4]([O:3][P:1]([O:19][CH2:20][C:21]([CH3:26])([CH3:25])[CH2:22][C:23]([OH:28])=[O:24])([O:11][CH2:12][C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)=[O:2])[C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1

Participants

5

Reactant 3

HCID 311Citric AcidHCID 2724130Cornforth reagentHCID 54009748Dibenzyl 4-hydroxy-2,2-dimethylbutyl phosphate

Product 1

HCID 540936554-{[Bis(benzyloxy)phosphoryl]oxy}-3,3-dimethylbutanoic acidYield 85.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of the product from Example 9B (0.396 g, 1.0 mmol) in DMF (10 mL) at room temperature was added pyridinium dichromate (2.3 g), and the mixture was stirred for 48 hours. 10% citric acid was added and the reaction was extracted twice with ethyl acetate. The combined organic layer was washed with brine, dried over MgSO4, filtered and evaporated. The residue was purified by chromatography on silica gel, eluting with a gradient of 0-5% methanol in chloroform, to give the title compound (0.334 g, 81%).

Workup

  1. extractionthe reaction was extracted twice with ethyl acetate
  2. washThe combined organic layer was washed with brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. customevaporated
  6. customThe residue was purified by chromatography on silica gel
  7. washeluting with a gradient of 0-5% methanol in chloroform

Sources & evidence

ORD record
ord-c49d69730f1c4e409055f192f5b34435
Source dataset
uspto-grants-2013_04
Patent number
US08426388B2

Reaction notes

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