Nouri Dustin H, Tantillo Dean J
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, USA.
J Org Chem. 2006 May 12;71(10):3686-95. doi: 10.1021/jo052498z.
An unusual reaction manifold for cyclopropylcarbinyl cations, uncovered using B3LYP and MP2 calculations, is described. This reaction is a hybrid of a [1,2] sigmatropic hydrogen shift and a two-electron electrocyclic ring opening. These two processes occur through a single transition structure (i.e., they are concerted), although they are not synchronous. We call these reactions "hiscotropic" rearrangements. The potential energy surfaces for these reactions are often complicated, in some cases involving flat plateaus and bifurcations. Torquoselectivity occurs in some cases as a result of favorable orbital interactions between the breaking C-C and C-H bonds.
描述了一种使用B3LYP和MP2计算发现的环丙基碳正离子不同寻常的反应历程。该反应是[1,2] 迁移氢迁移和双电子电环化开环的混合反应。这两个过程通过单一过渡结构发生（即它们是协同的），尽管它们并不同步。我们将这些反应称为“各向同性”重排。这些反应的势能面通常很复杂，在某些情况下涉及平坦的高原和分支。在某些情况下，由于断裂的C-C键和C-H键之间有利的轨道相互作用，会出现扭转选择性。
