顺式双环[4.2.0]辛-7-烯热解旋电环化异构化为顺式，顺式-1,3-环辛二烯。

Thermal disrotatory electrocyclic isomerization of cis-bicyclo[4.2.0]oct-7-ene to cis,cis-1,3-cyclooctadiene.

作者信息

Baldwin John E, Gallagher Sarah S, Leber Phyllis A, Raghavan Anuradha

机构信息

Department of Chemistry, Syracuse University, Syracuse, New York 13244, USA.

出版信息

Org Lett. 2004 Apr 29;6(9):1457-60. doi: 10.1021/ol040022g.

DOI:10.1021/ol040022g

PMID:15101766

Abstract

[reaction: see text] The ratio of observed rate constants, k/k', for thermal isomerizations of cis-bicyclo[4.2.0]oct-7-ene and its 2,2,5,5-d(4) analogue to cis,cis-1,3-cyclooctadienes at 250 degrees C is 1.17, indicative of a secondary, not a primary, deuterium kinetic isotope effect. The reaction does not occur through a [1,5] hydrogen shift from the transient cis,trans-1,3-cyclooctadiene intermediate to form the observed cis,cis-diene product.

摘要

[反应：见正文] 在250℃下，顺式双环[4.2.0]辛-7-烯及其2,2,5,5-d(4)类似物热异构化为顺,顺-1,3-环辛二烯的观测速率常数之比k/k'为1.17，这表明存在二级而非一级氘动力学同位素效应。该反应不是通过从瞬态顺,反-1,3-环辛二烯中间体进行[1,5]氢迁移来形成观测到的顺,顺-二烯产物。