tert-Butyl hydroperoxide → 4-Methoxybenzyl 2-(acetoxymethyl)-5-[[bis(allyloxy)phosphoryl]oxymethyl]benzoate

HRID 1766858Notes

Reaction equation

HRID 1766858 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH:23]=[CH:22][C:21]([CH2:24][OH:25])=[CH:20][C:7]=1[C:8]([O:10][CH2:11][C:12]1[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[CH:14][CH:13]=1)=[O:9])(=[O:3])[CH3:2].N1C=NN=N1.[CH2:31]([O:34][P:35]([O:43][CH2:44][CH:45]=[CH2:46])N(C(C)C)C(C)C)[CH:32]=[CH2:33].C([O:51]O)(C)(C)C.C(=O)([O-])O.[Na+].S([O-])([O-])(=O)=S.[Na+].[Na+]>ClCCl.CO.CCCCCC.C(OCC)(=O)C>[C:1]([O:4][CH2:5][C:6]1[CH:23]=[CH:22][C:21]([CH2:24][O:25][P:35]([O:34][CH2:31][CH:32]=[CH2:33])([O:43][CH2:44][CH:45]=[CH2:46])=[O:51])=[CH:20][C:7]=1[C:8]([O:10][CH2:11][C:12]1[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[CH:14][CH:13]=1)=[O:9])(=[O:3])[CH3:2]

Participants

11

Reactant 6

HCID 6410tert-Butyl hydroperoxideHCID 24477Sodium ThiosulfateHCID 516892Sodium BicarbonateHCID 4686855Diallyl diisopropylphosphoramiditeHCID 178625854-Methoxybenzyl 2-(acetoxymethyl)-5-(hydroxymethyl)benzoateHCID 178418441HCID 178418441, compound

Product 1

HCID 178625614-Methoxybenzyl 2-(acetoxymethyl)-5-[[bis(allyloxy)phosphoryl]oxymethyl]benzoateYield 85%

Reagents, catalysts & solvents 4

HCID 887MethanolCatalystHCID 6344DichloromethaneSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 4-methoxybenzyl 2-(acetoxymethyl)-5-(hydroxymethyl)benzoate (480.4 mg, 1.40 mmol) obtained from Example 1-(9) in dichloromethane (10 ml) was cooled to 0° C., and then tetrazole (195.4 mg, 2.79 mmol) and bis(allyloxy)(diisopropylamino)phosphine (Tetrahedron Lett., 30, 4219 (1989); 444.9 mg, 1.82 mmol) were added thereto with stirring, followed by stirring the mixture at the same temperature for 15 minutes. After the reaction mixture was warmed to room temperature and stirred for 1 hour, methanol (12 drops) was added thereto. The mixture was stirred for 5 minutes and then cooled to 0° C., and tert-butyl hydroperoxide (80% di-tert-butyl peroxide solution; Merck; 0.54 g, 4.8 mmol) was added thereto, then the mixture was warmed to room temperature and stirred for 15 minutes. A saturated aqueous solution of sodium hydrogen carbonate and an aqueous solution of sodium thiosulfate were added thereto, and the mixture was stirred for 10 minutes and partitioned between ethyl acetate and water. The obtained organic layers were combined and the solvent was distilled off under reduced pressure to give an oily residue. The residue was subjected to chromatography on a silica gel (25 g) column (eluent; ethyl acetate:hexane=1:2˜1:1) to afford the title compound (598.3 mg, 85% yield) as a colorless oil.

Workup

  1. stirringby stirring the mixture at the same temperature for 15 minutes
  2. temperatureAfter the reaction mixture was warmed to room temperature
  3. stirringstirred for 1 hour
  4. stirringThe mixture was stirred for 5 minutes
  5. temperaturecooled to 0° C.
  6. temperaturethe mixture was warmed to room temperature
  7. stirringstirred for 15 minutes
  8. stirringthe mixture was stirred for 10 minutes
  9. custompartitioned between ethyl acetate and water
  10. distillationthe solvent was distilled off under reduced pressure
  11. customto give an oily residue

Sources & evidence

ORD record
ord-f5a8e938311c4e15b5603eac972c9302
Source dataset
uspto-grants-2007_06
Patent number
US07230023B2

Reaction notes

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