title: Dynamics and a unified understanding of competitive [2,3]- and [1,2]-sigmatropic rearrangements based on a study of ammonium ylides.
abstract: 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.
authors.affiliation: Department of Chemistry, Texas A&M University , P.O. Box 30012, College Station, Texas 77842, United States.
authors.forename: Bibaswan
authors.initials: B
authors.lastname: Biswas
authors.forename: Sean C
authors.initials: SC
authors.lastname: Collins
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Singleton
mesh_terms: D064751:Ammonium Compounds / Q000737:chemistry*; D008958:Models, Molecular; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D064751:Ammonium Compounds