手性助剂诱导下的α,β-不饱和酮的不对称加氢反应及其在合成(R)-麝香酮中的应用  

Asymmetric Hydrogenation of α,β Unsaturated Ketones in the Presence of Chiral Auxiliaries—Preparation of ( R ) Muscone

作　　者：谢宝汉[1] 吕士杰[1] 高兰云[1] 傅宏祥[1] 

机构地区：[1]中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室

出　　处：《分子催化》1997年第6期433-438,共6页Journal of Molecular Catalysis(China)

摘　　要：在ＴＨＦ溶液中，４０－６０℃及０．３－０．５ＭＰａ氢压条件下，［ＲｕＣｌ２（ｃｈｔ）］２＋（Ｓ）－ＢＩＮＡＰ手性催化剂体系催化不饱和手性缩酮２选择加氢，再经脱去手性二醇，即可高立体选择性地制得（Ｒ）－３－甲基环十五烷酮（４，（Ｒ）－（－）－麝香酮），化学收率≥９５％，光学纯度≥９７％．手性缩酮２由Ｄ－苏糖醇或Ｄ－葡萄糖衍生的手性二醇３与３－甲基环十五烯－２－酮１生成．Asymmetric hydrogenation of α,β unsaturated ketones is a great challenge to synthetic chemists. In this paper a novel process was presented. Chiral alcohols ( 3 ) from tartaric acid or glucose react with 3 methyl 2 cyclopentadecen 1 one ( 1 ) to form unsaturated chiral ketal ( 2 ). In the presence of another chiral catalysts, like [RuCl 2(cht)] 2 [( S ) BINAP], hydrogenation of the chiral ketals ( 2 ) produces, after the release of chiral alcohol, ( R ) muscone with high optical yield (98% e.e.) and good chemical yield (97%) under the conditions of THF, 50℃, 0.3 MPa for 40 h.

关 键 词：不饱和酮 不对称氢化 (R)-麝香酮 麝香酮 

分 类 号：R284.3[医药卫生—中药学]