Citric Acid → 4-{[Bis(benzyloxy)phosphoryl]oxy}-2,2-dimethylbutanoic acid

HRID 1968915Notes

Reaction equation

HRID 1968915 reaction equation
[P:1]([O:19][CH2:20][CH2:21][C:22]([CH3:26])([CH3:25])[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][CH2:21][C:22]([CH3:26])([CH3:25])[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 67234826Dibenzyl 4-hydroxy-3,3-dimethylbutyl phosphate

Product 1

HCID 672351544-{[Bis(benzyloxy)phosphoryl]oxy}-2,2-dimethylbutanoic acidYield 89.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of the product from Example 11A (0.922 g, 2.4 mmol) in DMF (20 mL) at room temperature was added pyridinium dichromate (5.5 g), and the mixture was stirred for 16 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 starting with chloroform and ending with 5% methanol in chloroform, to give the title compound (0.839 g, 88%).

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

Sources & evidence

ORD record
ord-a4d5ee13ea314ee59c9741aa50b680ff
Source dataset
uspto-grants-2013_04
Patent number
US08426388B2

Reaction notes

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