Methanol → HCID 70281582, compound

HRID 1637396Notes

Reaction equation

HRID 1637396 reaction equation
[CH3:1][CH2:2][C:3](=[O:29])[C:4]1[C@:21]2([CH3:22])[C@H:7]([C@H:8]3[C@H:18]([C@@H:19]([O:23][Si:24]([CH3:27])([CH3:26])[CH3:25])[CH2:20]2)[C@:16]2([CH3:17])[C:11](=[CH:12][C:13](=[O:28])[CH:14]=[CH:15]2)[CH2:10][CH2:9]3)[CH2:6][CH:5]=1.Cl[Si:31]([CH3:34])([CH3:33])[CH3:32].CO.[CH3:37]CN(CC)CC.OP([O-])(O)=O.[K+]>C1COCC1.CCOC(C)=O.O>[CH3:37][C@@H:5]1[CH2:6][C@@H:7]2[C@:21]([CH3:22])([CH2:20][C@H:19]([O:23][Si:24]([CH3:25])([CH3:27])[CH3:26])[C@H:18]3[C@H:8]2[CH2:9][CH2:10][C:11]2[C@:16]3([CH3:17])[CH:15]=[CH:14][C:13](=[O:28])[CH:12]=2)[C:4]1=[C:3]([O:29][Si:31]([CH3:34])([CH3:33])[CH3:32])[CH2:2][CH3:1]

Participants

9

Reactant 5

HCID 887MethanolHCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 516951Monobasic potassium phosphateHCID 10573746HCID 10573746, compound

Product 1

HCID 70281582HCID 70281582, compoundYield 85.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred, cooled (-45° C. bath, MeCN--CO2) solution of 21-methyl-11β-(trimethylsiloxy)-pregna-1,4,16-trien-3,20-dione (0.395 g, 0.96 mmol) in 9.0 mL of anhydrous THF under Ar was added via syringe chlorotrimethylsilane (0.50 mL, 4.0 mmol), followed by dropwise addition over 3 min of 5.0 mL (1.0 mmol) of the above cuprate solution. After 10 min, the mixture was quenched at -45° C. (bath) by rapid addition via syringe of a solution of 0.5 mL (12 mmol) of MeOH and 1.5 mL (11 mmol) of Et3N and warming to 0° C. Water and EtOAc were added and the solution was stirred vigorously. The pH was adjusted from 9 to 7 with sat. KH2PO4 and stirring was continued for 0.5 h. The layers were separated and the organic solution was washed with water and brine, dried (MgSO4), filtered and concentrated. The residue was purified by chromatography to give 0.41 g (85.5%) of the desired product, C29H48O3Si2, as a white solid.

Workup

  1. customthe mixture was quenched at -45° C. (bath)
  2. stirringstirring
  3. waitwas continued for 0.5 h
  4. customThe layers were separated
  5. washthe organic solution was washed with water and brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by chromatography

Sources & evidence

ORD record
ord-136820d7e59b4a5e885467e814a5935a
Source dataset
uspto-grants-2000_03
Patent number
US06040468

Reaction notes

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