过氧酸对烯烃的环氧化反应：从教科书机理到量子力学推导的弯箭头描述

Klein Johannes E M N, Knizia Gerald, Rzepa Henry S

Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering University of Groningen Nijenborgh 4 9747 AG Groningen The Netherlands.

Department of Chemistry Pennsylvania State University 401A Chemistry Bldg; University Park PA 16802 USA.

ChemistryOpen. 2019 Jul 12;8(10):1244-1250. doi: 10.1002/open.201900099. eCollection 2019 Oct.

Using the intrinsic bond orbital (IBO) analysis based on accurate quantum mechanical calculations of the reaction path for the epoxidation of propene using peroxyacetic acid, we find that the four commonly used curly arrows for representing this reaction mechanism are insufficient and that seven curly arrows are required as a result of changes to σ and π bonding interactions, which are usually neglected in all textbook curly arrow representations. The IBO method provides a convenient quantitative method for deriving curly arrows in a rational manner rather than the normal representations used ubiquitously in teaching organic chemistry.

通过基于对过氧乙酸环氧化丙烯反应路径进行精确量子力学计算的内禀键轨道（IBO）分析，我们发现用于表示该反应机理的四个常用弯箭头并不充分，由于σ键和π键相互作用的变化，需要七个弯箭头，而这些相互作用在所有教科书的弯箭头表示中通常被忽略。IBO方法提供了一种方便的定量方法，以合理的方式推导弯箭头，而不是有机化学教学中普遍使用的常规表示方法。