Potential surface for the quadruply degenerate rearrangement of bicyclo[3.1.0]hex-2-ene

被引：31

作者：

Suhrada, CP ^{[1
]}

Houk, KN ^{[1
]}

机构：

[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 30期

关键词：

D O I：

10.1021/ja020601l

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Previous experimental studies have shown that bicyclo[3.1.0]hex-2-ene and substituted derivatives undergo thermal rearrangements to form three products identical to the starting material save for the position of the labeling substituents. Despite the likely involvement of a symmetric diradical intermediate, cyclohexene-3,5-diyl, these products are formed at unequal rates. DFT (B3LYP), CASSCF, and CASPT2 calculations were performed to map out the details of the potential energy landscape for the reaction. A qualitative hypothesis, based on dynamical considerations, is offered to explain the observed nonstatistical product distribution. Copyright © 2002 American Chemical Society.

引用

页码：8796 / 8797

页数：2

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