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

Abstract

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 Møller–Plesset calculations. [1,2]Migration, [2,3]sigmatropic rearrangement, β-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.