Homolysis of allyloxy(hydroxy)carbene.: A density functional theory and ab initio study

被引：13

作者：

Reid, DL ^{[1
]}

Warkentin, J ^{[1
]}

机构：

[1] McMaster Univ, Dept Chem, Hamilton, ON L8S 4M1, Canada

来源：

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 2000年 / 09期

关键词：

D O I：

10.1039/b001033m

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Warkentin and Venneri have shown that the bulk of the rearrangement products of allyloxy(methoxy)carbenes result from a homolysis-recoupling mechanism in contrast to the known cases of [2,3]sigmatropic rearrangements of analogous (bisheteroatom)carbenes (J. Am. Chem. Soc., 1998, 120, 11182). Herein, allyloxy(hydroxy)carbene is used as a model to investigate the fragmentations with density functional and Moller-Plesset calculations. [1,2]Migration, [2,3]sigmatropic rearrangement, beta-scission from the triplet, and homolysis from the singlet state are all examined. Homolysis of singlet allyloxy(hydroxy)carbene is shown to be a viable pathway, and is best able to explain the experimental results.

引用

页码：1980 / 1983

页数：4

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