p-Toluenesulfonic acid → (1R,2R)-1-[3-(tertbutyldiphenylsilyloxy)benzyl]-1,2-dihydroxycyclohexane

HRID 379312Notes

Reaction equation

HRID 379312 reaction equation
CC1(C)[O:6][C@@H:5]2[CH2:7][CH2:8][CH2:9][CH2:10][C@:4]2([CH:11](O)[C:12]2[CH:13]=[C:14]([O:18][Si:19]([C:32]([CH3:35])([CH3:34])[CH3:33])([C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=3)[C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[CH:15]=[CH:16][CH:17]=2)[O:3]1.C1C=CC(OC(Cl)=S)=CC=1.N(C(C)(C)C#N)=NC(C)(C)C#N.C1(C)C=CC(S(O)(=O)=O)=CC=1>C(Cl)Cl.C1(C)C=CC=CC=1.C([SnH](CCCC)CCCC)CCC.CO.C1COCC1.N1C=CC=CC=1>[C:32]([Si:19]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)([C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)[O:18][C:14]1[CH:13]=[C:12]([CH:17]=[CH:16][CH:15]=1)[CH2:11][C@:4]1([OH:3])[CH2:10][CH2:9][CH2:8][CH2:7][C@H:5]1[OH:6])([CH3:35])([CH3:33])[CH3:34]

Participants

11

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 6547AzobisisobutyronitrileHCID 70498Phenyl thioxochloroformateHCID 206917043-[((3aR,7aR)-2,2-dimethyl-hexahydro-1,3-benzodioxol-3a-yl) hydroxymethyl]-1-(tertbutyldiphenyl-silyloxy)benzene

Product 1

HCID 20691700(1R,2R)-1-[3-(tertbutyldiphenylsilyloxy)benzyl]-1,2-dihydroxycyclohexaneYield 74.8%

Reagents, catalysts & solvents 6

HCID 887MethanolSolventHCID 1049PyridineSolventHCID 1140TolueneSolventHCID 5948TributylstannaneSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 3-[((3aR,7aR)-2,2-dimethyl-hexahydro-1,3-benzodioxol-3a-yl) hydroxymethyl]-1-(tertbutyldiphenyl-silyloxy)benzene (45 g) in CH2Cl2 (450 ml) were added phenyl chlorothionoformate (14.5 ml) and pyridine (18 ml) at 0° C. After being stirred for 12 hours at room temperature, the mixture was evaporated and the resultant was partitioned between EtOAc and water. The organic layer was washed with water, 1N-HCl solution, sat.NaHCO3 solution and then brine. The solvent was evaporated in vacuo to give an oily residue. The residue was dissolved in toluene (400 ml) to which tributyltinhydride (50 ml) and 2,2′-azobis-(isobutyronitrile)(100 mg) were added. The mixture was refluxed for 4 hours under stirring and then purified by chromatography on silica gel to give an oily compound. The oily compound was dissolved in a mixture of MeOH (200 ml) and THF (100 ml), to which p-toluenesulphonic acid (200mg) was added at room temperature. The mixture was stirred for 12 hours and evaporated. The residue was partitioned between EtOAc and water. The organic layer was washed with water, sat. NaHCO3 solution and then brine. The solvent was evaporated in vacuo to give (1R,2R)-1-[3-(tertbutyldiphenylsilyloxy)benzyl]-1,2-dihydroxycyclohexane (30 g).

Workup

  1. customthe mixture was evaporated
  2. customthe resultant was partitioned between EtOAc and water
  3. washThe organic layer was washed with water, 1N-HCl solution
  4. customThe solvent was evaporated in vacuo
  5. customto give an oily residue
  6. additionwere added
  7. temperatureThe mixture was refluxed for 4 hours
  8. stirringunder stirring
  9. custompurified by chromatography on silica gel
  10. customto give an oily compound
  11. additionwas added at room temperature
  12. stirringThe mixture was stirred for 12 hours
  13. customevaporated
  14. customThe residue was partitioned between EtOAc and water
  15. washThe organic layer was washed with water, sat. NaHCO3 solution
  16. customThe solvent was evaporated in vacuo

Sources & evidence

ORD record
ord-bddf0593e23e4af9993784d751d442f2
Source dataset
uspto-grants-2001_10
Patent number
US06297267B1

Reaction notes

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