Triethylamine → 17-Acetylthiomethyl-1alpha,3beta-bis(tert-butyldimethylsilyloxy)androsta-5,7,16-triene

HRID 1792168Notes

Reaction equation

HRID 1792168 reaction equation
[Si:1]([O:8][C@@H:9]1[C@@:26]2([CH3:27])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:25]2[CH2:24][CH2:23][C@@:21]2([CH3:22])[C@H:17]3[CH2:18][CH:19]=[C:20]2[CH2:28]O)[CH2:12][C@@H:11]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C(N(CC)CC)C.CS(Cl)(=O)=O.[C:50]([O-:53])(=[S:52])[CH3:51].[K+]>O1CCCC1.CS(C)=O.CCCCCC>[C:50]([S:52][CH2:28][C:20]1[C@:21]2([CH2:23][CH2:24][C@H:25]3[C:16](=[CH:15][CH:14]=[C:13]4[C@:26]3([CH3:27])[C@@H:9]([O:8][Si:1]([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:2])[CH3:3])[CH2:10][C@H:11]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:32])[CH3:33])[CH2:12]4)[C@@H:17]2[CH2:18][CH:19]=1)[CH3:22])(=[O:53])[CH3:51]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 23670855Potassium ethanethioateHCID 673014381alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17-(hydroxymethyl)androsta-5,7,16-triene

Product 1

HCID 8658997017-Acetylthiomethyl-1alpha,3beta-bis(tert-butyldimethylsilyloxy)androsta-5,7,16-trieneYield 88.3%

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

To a solution of 1α,3β-bis(tert-butyldimethylsilyloxy)-17-(hydroxymethyl)androsta-5,7,16-triene (4.00 g, 7.34 mmol) in tetrahydrofuran (70 ml), was added triethylamine (4.10 ml, 29.4 mmol), followed by the dropwise addition of methanesulfonyl chloride (1.70 ml, 22.0 mmol) at −10° C. and stirring for 20 min. The reaction mixture was warmed to room temperature and a solution of potassium thioacetate (3.73 g, 29.4 mmol) in dimethylsulfoxide (70 ml) was added. After stirring for 30 min., the mixture was diluted with hexane, washed with water, the organic layer was dried over anhydrous magnesium sulfate and evaporated for removing the solvent. The thus obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate=15:1) to give the titled compound (3.91 g, 88%) as a colorless oil.

Workup

  1. stirringAfter stirring for 30 min.
  2. washwashed with water
  3. dry with materialthe organic layer was dried over anhydrous magnesium sulfate
  4. customevaporated
  5. customfor removing the solvent
  6. customThe thus obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate=15:1)

Sources & evidence

ORD record
ord-399cca0fbbf6451b89afcb477ad98cfd
Source dataset
uspto-grants-2006_07
Patent number
US07074777B2

Reaction notes

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