应用量子化学反应性指数研究频哪醇重排反应  

Study on the Rearrangement of Pinacol by Quantum Chemical Reactivity Index

作　　者：张军军 白育庭 邵开元 胡文祥 Zhang Junjun;Bai Yuting;Shao Kaiyuan;Hu Wenxiang(School of Pharmacy,Hubei University of Science and Technology,Xianning,437100;Jingdong Xianghu Microwave Chemistry Union Laboratory,Beijing Excalibur Space Military Academy of Medical Sciences,Beijing,101601;Aerospace Systems Division,Strategic Support Troops,Chinese People’s Liberation Army,Beijing,100101)

机构地区：[1]湖北科技学院药学院,咸宁437100 [2]北京神剑天军医学科学院京东祥鹄微波化学联合实验室,北京101601 [3]中国人民解放军战略支援部队航天系统部,北京100101

出　　处：《化学通报》2020年第8期747-754,共8页Chemistry

摘　　要：1,2-二醇类化合物的频哪醇重排反应是经典的化学重排反应。无环的或环状的1,2-二醇类化合物在质子酸或路易斯酸的作用下会重排发生取代基的1,2-迁移,其产物往往伴随不同基团的迁移而生。但是,主产物取决于二羟基相连接的碳原子上取代基的空间架构和性质。本文采用净亲电指数(Multiphilic index)和Wiberg键级等量子化学反应性指数来定量描述1,2-二醇类化合物的频哪醇重排反应机理,并依此作为预测频哪醇反应主产物的依据。Pinacol rearrangement of 1,2-diols is a classical chemical rearrangement.Including acyclic and cyclic 1,2-diols,under the action of protonic acid or Lewis acid,the 1,2-transfer of substituents occurs,and the products are often generated with the migration of different groups.However,the main product depends on the spatial structure and properties of the substituents on the dihydroxy linked carbon atoms.In this paper,the mechanism of pinacol rearrangement of 1,2-diols is quantitatively described by using the net electrophilic index(Multiphilic index),Wiberg bond index and other quantum chemical reactivity indexes,which can be used as the basis for predicting the main products of pinacol rearrangement.

关 键 词：频哪醇重排反应 量子化学反应性指数 净亲电指数 Wiberg键级 反应机理 

分 类 号：O621.25[理学—有机化学]