DYNAMIC MATCHING - THE CAUSE OF INVERSION OF CONFIGURATION IN THE [1,3] SIGMATROPIC MIGRATION

被引：144

作者：

CARPENTER, BK

机构：

[1] Department of Chemistry, Baker Laboratory, Cornell University, Ithaca

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1995年 / 117卷 / 23期

关键词：

D O I：

10.1021/ja00128a024

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Direct dynamics calculations using the PM3 semiempirical molecular orbital method are carried out on the formal [1,3] sigmatropic migration that interconverts bicyclo[3.2.0]hept-2-ene and norbornene. Methylated analogs are also investigated. It is shown that, despite the existence of a 5 kcal/mol local minimum corresponding to a biradical intermediate on the PM3 potential energy surface for the reaction, the transformation still occurs with a preference for inversion of configuration at the migrating carbon. This stereoselectivity is dynamic in origin and has nothing to do with conservation of orbital symmetry. It can be overcome with a suitably placed methyl substituent. asis observed experimentally. The calculations result in movies that the reader can find on the World Wide Web (http://www.chem.cornell.edu/bkc1/Sigmatrophy.html). The implications of the calculations for the mechanisms of nominal [1,n] sigmatropic shifts of carbon are discussed.

引用

页码：6336 / 6344

页数：9

共 35 条

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