Hydrogen Peroxide → (3 R,4S,7S) 3,7-dibenzyloxy-4-vinyl-1,1-dimethoxydodeca-5-ene

HRID 258449Notes

Reaction equation

HRID 258449 reaction equation
[N+](C1C=CC=CC=1[Se]C#N)([O-])=O.[CH2:13]([O:20][C@@H:21]([C@@H:28]([CH2:45][CH2:46]O)[CH:29]=[CH:30][C@@H:31]([O:37][CH2:38][C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1)[CH2:32][CH2:33][CH2:34][CH2:35][CH3:36])[CH2:22][CH:23]([O:26][CH3:27])[O:24][CH3:25])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.C(P(CCCC)CCCC)CCC.OO>O1CCCC1>[CH2:13]([O:20][C@@H:21]([C@@H:28]([CH:45]=[CH2:46])[CH:29]=[CH:30][C@@H:31]([O:37][CH2:38][C:39]1[CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=1)[CH2:32][CH2:33][CH2:34][CH2:35][CH3:36])[CH2:22][CH:23]([O:26][CH3:27])[O:24][CH3:25])[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1

Participants

6

Reactant 4

HCID 784Hydrogen PeroxideHCID 13831TributylphosphineHCID 1039312-Nitrophenyl selenocyanateHCID 67862831(3R,4S,7S) 3,7-dibenzyloxy-4-(2'-hydroxyethyl)-1,1-dimethoxydodeca-5-ene

Product 1

HCID 67862608(3 R,4S,7S) 3,7-dibenzyloxy-4-vinyl-1,1-dimethoxydodeca-5-eneYield 91%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of 997 mg (3.67 mM) of o-nitrophenylselenium cyanide in 12 ml of anhydrous tetrahydrofuran was dropwise added 886 mg (1.83 mM) of (3R,4S,7S) 3,7-dibenzyloxy-4-(2'-hydroxyethyl)-1,1-dimethoxydodeca-5-ene [7] described above. The mixture was stirred for several minutes and 0.91 ml (3.67 mM) of tri-n-butylphosphine was dropwise added to the mixture. The reaction solution was stirred for ten minutes then cooled to 0° C. and 35% hydrogen peroxide aqueous solution was dropwise added thereto at the same temperature while stirring. After stirring for 3 hours, the aqueous phase was extracted with a solvent mixture of diethyl ether:hexane=7:3. The extracts were combined and washed sequentially with saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The precipitated crystals were taken from the residue by filtration to give 776 mg (1.67 mM) of (3R,4 S,7S) 3,7-dibenzyloxy-4-vinyl-1,1-dimethoxydodeca-5-ene [8]. Yield, 91%.

Workup

  1. stirringThe reaction solution was stirred for ten minutes
  2. stirringat the same temperature while stirring
  3. stirringAfter stirring for 3 hours
  4. extractionthe aqueous phase was extracted with a solvent mixture of diethyl ether
  5. washwashed sequentially with saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution
  6. dry with materialAfter drying over anhydrous magnesium sulfate
  7. distillationthe solvent was distilled off under reduced pressure
  8. filtrationThe precipitated crystals were taken from the residue by filtration

Sources & evidence

ORD record
ord-486a94eadf0f478f89dbf7df18e75c3e
Source dataset
uspto-grants-1993_11
Patent number
US05266703

Reaction notes

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