Dynamics and a Unified Understanding of Competitive [2,3]- and [1,2]-Sigmatropic Rearrangements Based on a Study of Ammonium Ylides

[Image: see text] The [2,3]- and [1,2]-sigmatropic rearrangements of ammonium ylides are studied by a combination of experimental, standard computational, and dynamic trajectory methods. The mixture of concerted [2,3] rearrangement and bond cleavage observed experimentally is accounted for by the outcome of trajectories passing through the formal [2,3] rearrangement transition state. In this way the bond cleavage is promoted by the pericyclic stabilization of the [2,3] transition state. It is proposed that this dynamic effect is responsible for the pervasive co-occurrence of the two rearrangements.