A DFT study on the thermal aryl migration in aryliodonium ylides. Support for a concerted mechanism

J Org Chem. 2006 Sep 1;71(18):7060-2. doi: 10.1021/jo0610964.

Abstract

A DFT study on the intramolecular thermal phenyl migration in iodonium ylides supports a concerted mechanism. In contrast to the two, different than each other, suggested mechanisms, involving only intermediates, this study indicates a single-step, transition-state one--involving a five-membered cyclic ring--with no intermediates. The frontier-orbital-controlled migration also confirms the different thermal behavior of two different ylides.