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化学进展 2012, Vol. 24 Issue (06): 879-885 前一篇   后一篇

• 量子化学专辑 •

[2+2]环加成反应机理的理论研究

方德彩*   

  1. 北京师范大学化学学院 北京 100875
  • 收稿日期:2012-12-01 修回日期:2012-03-01 出版日期:2012-06-24 发布日期:2012-05-11
  • 通讯作者: 方德彩 E-mail:dcfang@bnu.edu.cn
  • 基金资助:

    国家自然科学基金项目(No. 21073016)和教育部博士点基金(No.20090003110008)资助

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Theoretical Studies on the Mechanisms of [2+2] Cycloaddition Reactions

Fang Decai   

  1. College of Chemistry, Beijing Normal University, Beijing 100875, China
  • Received:2012-12-01 Revised:2012-03-01 Online:2012-06-24 Published:2012-05-11
[2+2]环加成反应是有机化学中非常重要的一类反应,其机理的研究一直是实验和理论工作者关注的课题之一。本文从理论的角度综述了三类[2+2]环加成反应的反应机理,即简单烯烃或炔烃参与的环加成反应、累积双键体系参与的环加成反应以及稀土钍化合物参与的环加成反应, 得出对于简单的烯烃或炔烃之间的环加成反应一般是按双自由基机理进行,而其他两类反应主要按协同或两性离子方式进行,并且从前线分子轨道作用理论角度分析了产生不同反应机理的原因。
关键词： 环加成反应, 累积双键体系, 双自由基机理, 协同机理, 两性离子
[2+2] cycloaddition reaction is one type of the most important reactions in the field of organic chemistry, and the mechanisms of [2+2] cycloaddition reactions are always hot topic both for experimental and theoretical researchers. In this paper, three types of [2+2] cycloaddition reactions, including simple olefins or alkynes, cumulenes, Th compounds, have been classified and reviewed. The obtained results indicated that the cycloaddition reactions involving simple olefins or alkynes are proceeding in diradical mechanism generally, and the others are proceeding in either concerted or zwitterion mechanism, all of which have been elucidated with frontier molecular orbital interactions. Contents
1 Introduction
2 [2+2] cycloaddition reactions of olefins or alkynes
3 [2+2] cycloaddition reactions of cumulenes X=Y=Z
3.1 [2+2] cycloaddition reactions of ketene
3.2 [2+2] cycloaddition reactions of keteniminium and 2-aza-allene cations
4 [2+2] cycloaddition reactions of Th-containing compounds
5 Conclusions and Outlooks
Key words: cycloaddition reaction, cumulenes, diradical, concerted, zwitterion

中图分类号: 

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[2+2]环加成反应机理的理论研究