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

HRID 1014966Notes

Reaction equation

HRID 1014966 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), triethylamine (4.10 ml, 29.4 mmol) was added and methanesulfonyl chloride (1.70 ml, 22.0 mmol) was further added dropwise at −10° C., followed by stirring for 20 minutes. After warming to room temperature, a solution of potassium thioacetate (3.73 g, 29.4 mmol) in dimethyl sulfoxide (70 ml) was added to the reaction mixture. The reaction mixture was stirred for 30 minutes, diluted with hexane, washed with water and then dried over anhydrous magnesium sulfate. After evaporation under reduced pressure to remove the solvent, the resulting 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. stirringThe reaction mixture was stirred for 30 minutes
  2. washwashed with water
  3. dry with materialdried over anhydrous magnesium sulfate
  4. customAfter evaporation under reduced pressure
  5. customto remove the solvent
  6. customthe resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=15:1)

Sources & evidence

ORD record
ord-5332aaacd798420fbad39b74a8fc728b
Source dataset
uspto-grants-2011_07
Patent number
US07985744B2

Reaction notes

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