Dynamics and a unified understanding of competitive [2,3]- and [1,2]-sigmatropic rearrangements based on a study of ammonium ylides. Academic Article uri icon


  • 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.

altmetric score

  • 20.456

author list (cited authors)

  • Biswas, B., Collins, S. C., & Singleton, D. A

citation count

  • 49

complete list of authors

  • Biswas, Bibaswan||Collins, Sean C||Singleton, Daniel A