反应详情

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).

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