Hexane → 1alpha,3beta-Bis(tert-butyldimethylsilyloxy)-20-oxopregna-5,7,16-triene

HRID 1014979Notes

Reaction equation

HRID 1014979 reaction equation
FC(F)(F)S(O[C:7]1[C@:8]2([CH2:25][CH2:24][C@H:23]3[C:13](=[CH:14][CH:15]=[C:16]4[C@:21]3([CH3:22])[C@@H:20]([O:26][Si:27]([C:30]([CH3:33])([CH3:32])[CH3:31])([CH3:29])[CH3:28])[CH2:19][C@H:18]([O:34][Si:35]([C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:37])[CH3:36])[CH2:17]4)[C@@H:10]2[CH2:11][CH:12]=1)[CH3:9])(=O)=O.[C]=[O:45].CCCC[CH2:50][CH3:51].[Cl-].C[Al+]C>CC(N(C)C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[Si:27]([O:26][C@@H:20]1[C@@:21]2([CH3:22])[C:16](=[CH:15][CH:14]=[C:13]3[C@@H:23]2[CH2:24][CH2:25][C@@:8]2([CH3:9])[C@H:10]3[CH2:11][CH:12]=[C:7]2[C:50](=[O:45])[CH3:51])[CH2:17][C@@H:18]([O:34][Si:35]([C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:36])[CH3:37])[CH2:19]1)([C:30]([CH3:32])([CH3:31])[CH3:33])([CH3:29])[CH3:28]

Participants

8

Reactant 4

HCID 8058HexaneHCID 16686359Dimethylalumanylium chlorideHCID 86590898(1alpha,3beta)-1,3-Bis((tert-butyl(dimethyl)silyl)oxy)androsta-5,7,16-trien-17-yl trifluoromethanesulfonateHCID 178418416HCID 178418416, compound

Product 1

HCID 120200821alpha,3beta-Bis(tert-butyldimethylsilyloxy)-20-oxopregna-5,7,16-trieneYield 100%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 31374DimethylacetamideSolvent

Procedure

(1α,3β)-1,3-Bis((tert-butyl(dimethyl)silyl)oxy)androsta-5,7,16-trien-17-yl trifluoromethanesulfonate (40.3 g) was dissolved in dimethylacetamide (203 ml), followed by addition of tetrakis(triphenylphosphine)palladium(0) (703 mg). The resulting mixture was placed under reduced pressure and then placed in a carbon monoxide atmosphere. This procedure was further repeated twice. A 0.98 M hexane solution of dimethylaluminum chloride (74.4 ml) was added to the mixture at room temperature and then stirred at room temperature for 20 minutes. After heating to 58° C. and stirring for 2 hours, water was added to the reaction mixture, which was then extracted with hexane/ethyl acetate=1/1. The extracted solution was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give the titled compound (34.0 g, yield 100%).

Workup

  1. temperatureAfter heating to 58° C.
  2. stirringstirring for 2 hours
  3. extractionwas then extracted with hexane/ethyl acetate=1/1
  4. dry with materialThe extracted solution was dried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-f7acd757742f42ffa28ec3640f4e6f84
Source dataset
uspto-grants-2011_07
Patent number
US07985744B2

Reaction notes

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