Tributylphosphine → 20-(5,5-Dimethyl-1,3-dioxan-2-yl)-1alpha,3beta-bis(methoxycarbonyloxy)pregn-5,7-diene

HRID 1196380Notes

Reaction equation

HRID 1196380 reaction equation
C(P(CCCC)CCCC)CCC.[CH3:14][C:15]1([CH3:57])[CH2:20][O:19][CH:18]([CH:21]([C@@H:23]2[C@:40]3([CH3:41])[C@H:26]([C@H:27]4[C@H:37]([CH2:38][CH2:39]3)[C@:35]3([CH3:36])[C:30]([CH2:31][C@@H:32]([O:47][C:48]([O:50][CH3:51])=[O:49])[CH2:33][C@@H:34]3[O:42][C:43]([O:45][CH3:46])=[O:44])=[CH:29][C@H:28]4OC(OC)=O)[CH2:25][CH2:24]2)[CH3:22])[O:17][CH2:16]1>O1CCOCC1>[CH3:57][C:15]1([CH3:14])[CH2:16][O:17][CH:18]([CH:21]([C@@H:23]2[C@:40]3([CH3:41])[C@H:26]([C:27]4[C@H:37]([CH2:38][CH2:39]3)[C@:35]3([CH3:36])[C:30]([CH2:31][C@@H:32]([O:47][C:48]([O:50][CH3:51])=[O:49])[CH2:33][C@@H:34]3[O:42][C:43]([O:45][CH3:46])=[O:44])=[CH:29][CH:28]=4)[CH2:25][CH2:24]2)[CH3:22])[O:19][CH2:20]1

Participants

4

Reactant 2

HCID 13831TributylphosphineHCID 5714185820-(5,5-Dimethyl-1,3-dioxan-2-yl)-1alpha,3beta,7alpha-tris(methoxycarbonyloxy)pregn-5-ene

Product 1

HCID 6785297120-(5,5-Dimethyl-1,3-dioxan-2-yl)-1alpha,3beta-bis(methoxycarbonyloxy)pregn-5,7-dieneYield 49.8%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Procedure

In 10 ml of dioxane was dissolved 25 mg of tris(dibenzylideneacetone)dipalladium(chloroform), followed by addition of 45 μl of tri-n-butylphosphine. The mixture was stirred in an atmosphere of argon gas at room temperature for 10 minutes. To this mixture was added a solution of 270 mg of 20-(5,5-dimethyl-1,3-dioxan-2-yl)-1α,3β,7α-tris(methoxycarbonyloxy)pregn-5-ene in 10 ml of dioxane and the mixture was refluxed for 12 hours. The resulting reaction mixture was cooled to room temperature and filtered with the aid of Florisil. The filtrate was concentrated under reduced pressure and the concentrate was purified by column chromatography. The procedure yielded 118 mg of 20-(5,5-dimethyl-1,3-dioxan-2-yl)-1α,3β-bis(methoxycarbonyloxy)pregna-5,7-diene showing the same physical properties as the compound obtained in Example 124.

Workup

  1. temperaturethe mixture was refluxed for 12 hours
  2. customThe resulting reaction mixture
  3. temperaturewas cooled to room temperature
  4. filtrationfiltered with the aid of Florisil
  5. concentrationThe filtrate was concentrated under reduced pressure
  6. customthe concentrate was purified by column chromatography

Sources & evidence

ORD record
ord-12c4d30ad3414b19b3853b0b3d450bf9
Source dataset
uspto-grants-1992_05
Patent number
US05112998

Reaction notes

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