Dimethyl Sulfoxide → (R)-1-[3-(tertbutyldiphenyl-silyloxy)benzyl]-1-trimethylsilyoxy-2-cyclohexanone

HRID 379313Notes

Reaction equation

HRID 379313 reaction equation
C(Cl)(C(Cl)=O)=O.CS(C)=O.[C:11]([Si:15]([C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)([C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[O:16][C:17]1[CH:18]=[C:19]([CH:29]=[CH:30][CH:31]=1)[CH2:20][C@:21]1([OH:28])[CH2:26][CH2:25][CH2:24][CH2:23][C@H:22]1[OH:27])([CH3:14])([CH3:13])[CH3:12].N1C=CN=C1>C(Cl)Cl.CN(C=O)C.C(N(CC)CC)C>[C:11]([Si:15]([C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)([C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1)[O:16][C:17]1[CH:18]=[C:19]([CH:29]=[CH:30][CH:31]=1)[CH2:20][C@:21]1([O:28][Si:15]([CH3:38])([CH3:32])[CH3:11])[CH2:26][CH2:25][CH2:24][CH2:23][C:22]1=[O:27])([CH3:14])([CH3:12])[CH3:13]

Participants

8

Reactant 4

HCID 679Dimethyl SulfoxideHCID 795ImidazoleHCID 65578Oxalyl chlorideHCID 20691700(1R,2R)-1-[3-(tertbutyldiphenylsilyloxy)benzyl]-1,2-dihydroxycyclohexane

Product 1

HCID 86757468(R)-1-[3-(tertbutyldiphenyl-silyloxy)benzyl]-1-trimethylsilyoxy-2-cyclohexanoneYield 16.6%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent2×HCID 8471TriethylamineSolvent

Procedure

To a solution of (COCl)2 (3.4 ml) in CH2Cl2 (100 ml) was dropwise added DMSO (3.7 ml) at −78° C. After 10minutes, a solution of (1R,2R)-1-[3-(tertbutyldiphenylsilyloxy)benzyl]-1,2-dihydroxycyclohexane (12 g) in CH2Cl2(50 ml) was added to the above mixture at the same temperature. After 10 minutes, the mixture was added with triethylamine (15 ml) and allowed to stand at room temperature. After evaporating the solvent, the residue was partitioned between EtOAc and water. The organic layer was washed with water and brine. The organic solvent was evaporated in vacuo to give an oily compound. The oily compound was dissolved in DMF (50 ml) and then added with trimethylsilychloride (6.6 ml) and imidazole(7.0 g) at room temperature. After stirring for 5 hours, the mixture was partitioned between EtOAc and water. The organic solvent was evaporated in vacuo. The residue was purified by chromatography on silica gel to give (R)-1-[3-(tertbutyldiphenylsilyloxy)benzyl]-1-trimethylsilyoxy-2-cyclohexanone (1.15 g).

Workup

  1. customat −78° C
  2. waitAfter 10 minutes
  3. customto stand at room temperature
  4. customAfter evaporating the solvent
  5. customthe residue was partitioned between EtOAc and water
  6. washThe organic layer was washed with water and brine
  7. customThe organic solvent was evaporated in vacuo
  8. customto give an oily compound
  9. customthe mixture was partitioned between EtOAc and water
  10. customThe organic solvent was evaporated in vacuo
  11. customThe residue was purified by chromatography on silica gel

Sources & evidence

ORD record
ord-91f65fd9404d4da1938e65b402e775b5
Source dataset
uspto-grants-2001_10
Patent number
US06297267B1

Reaction notes

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