[2,3]σ键迁移重排立体选择性的Huckel-Hubbard理论研究

本文提出一种确定Huckel-Hubbard(H-H)参数的方法,并将H-H 理论首次推广用于Witting重排,硫叶立德重排,烯丙基亚砜重排等2,3]σ键迁移重排反应的研究.我们考虑协同机理,构造了Huckel和Mobius 两种不同反应途径的基态和低激发态势能面,详细讨论了热反应和光化学反应的立体选择性和反应的活化能

Study of the stereoselectivity of [2,3] sigmatropic rearrangements based on Huckel-Hubbard theory

A method for determing Huckel-Hubbard (H-H) parameters was proposed, and the H-H theory is extended to analyze 2,3] sigmatropic rearrangements including Witting rearrangement, sulfur ylide rearrangement and allylic sulfoxide rearrangement. Taking the concerted mechanism into account, the ground state potential energy surface was constructed as well as the low-lying excited state ones for two different reaction pathways which correspond to Huckel mode and Mobius mode resp. The stereoselectivities of the thermal and photochem. processes as well as the activation energies were given and discussed in detail.e