含酯氧基手性方酰胺基醇催化前手性酮不对称还原反应机理的计算研究  

Computational Research on Asymmetric Rreduction of Prochiral Ketones Catalyzed by Chiral Cyclic Oxazaborolidines Containing Monoamidoalcohol Ester of Squaric Acid

作　　者：任译[1] 杨静[1] 刘玉明[2] 谢如刚[1] 

机构地区：[1]四川大学化学学院,成都610064 [2]四川大学分析测试中心,成都610064

出　　处：《四川大学学报（自然科学版）》2003年第3期517-520,共4页Journal of Sichuan University(Natural Science Edition)

基　　金：教育部回国人员科研启动基金

摘　　要：用量子化学半经验方法AM1对含酯氧基手性方酰胺基醇催化苯乙酮不对称还原的反应机理进行了计算研究,提出了合理的反应机理.结果表明,还原产物的手性是由口恶唑硼烷/硼烷/苯乙酮加合物及相继的六元环过渡态所决定的.根据过渡态理论,计算得到反映立体选择性大小的理论e.e.值.The Enantioselective borane reduction of prochiral aromatic ketones catalyzed by the newly catalystchiral cyclic oxazaborolidines containing monoamidoalcohol ester of squaric acid have been studied by the semiempirical method AM1. Reasonable mechanisms of the reaction have been suggested. The calculation results show that the chirality of the reductive product are determined by the oxazaborolidines/borane/acetophenone adduct and the followed sixmemberring transition state. The theoretical e.e. value calculated by the transition state theory can qualitatively describe the experimental results.

关 键 词：AM1 不对称催化 苯乙酮 还原 

分 类 号：O641.121[理学—物理化学] O643.12[理学—化学]