物理化学学报 >> 2002, Vol. 18 >> Issue (10): 890-895.doi: 10.3866/PKU.WHXB20021005

研究论文 上一篇    下一篇

噁唑硼烷催化芳醛不对称炔基化反应的量化研究

李明;何荣幸   

  1. 西南师范大学化学化工学院,重庆　400715
  • 收稿日期:2001-12-25 修回日期:2002-04-05 发布日期:2002-10-15
  • 通讯作者: 李明 E-mail:liming@swnu.edu.cn

Quantum Chemical Study on the Mechanism of Enantioselective Alkynylation of

Li Ming;He Rong-Xing   

  1. College of Chemistry and Chemical Engineering, Southwest-China Normal University, Chongqing　400715
  • Received:2001-12-25 Revised:2002-04-05 Published:2002-10-15
  • Contact: Li Ming E-mail:liming@swnu.edu.cn

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摘要： 对手性噁唑硼烷催化芳醛不对称炔基化还原反应的机理进行了量子化学半经验方法研究.研究表明,该反应是放热的，炔基转移是反应的控制步骤，炔基转移的过渡态具有扭曲的椅式结构，还原的主要产物是R-手性醇.

关键词: 手性噁唑硼烷, 不对称炔基化, 半经验方法, 芳香醛

Abstract: The semi empirical molecular orbital computations of the enontioselective alkynylation of benzaldehyde catalyzed by oxazaborolidine catalysts are performed. As illustrated, this enantioselective alkynylation reduction is exothermic and the controlling step is the transfer of alkynyl from the alkynylborane moiety to the carbonyl carbon of benzaldehyde. The transition state for the alkynyl transfer is a twisted chair structure. The alkynyl reduction leads to R-chiral alcohols.

Key words: Chiral oxazaborolidine, Enantioselective alkynylation, Semiempirical method, Benzaldehyde