Deconstructing Selectivity in the Gold-Promoted Cyclization of Alkynyl Benzothioamides to Six-Membered Mesoionic Carbene or Acyclic Carbene Complexes

by S.V.C. Vummaleti, L. Falivene, A. Poater, L. Cavallo
Year: 2014 ISSN: 21555435 DOI: 10.1021/cs5001575

Bibliography

Deconstructing Selectivity in the Gold-Promoted Cyclization of Alkynyl Benzothioamides to Six-Membered Mesoionic Carbene or Acyclic Carbene Complexes
S.V.C. Vummaleti, L. Falivene, A. Poater, L. Cavallo
ACS Catalysis 4, 1287, (2014)

Extra Information

ACS Catal.

Abstract

We demonstrate that the experimentally observed switch in selectivity from 5-exo-dig to 6-endo-dig cyclization of an alkynyl substrate, promoted by Au I and AuIII complexes, is connected to a switch from thermodynamic to kinetic reaction control. The AuIII center pushes alkyne coordination toward a single Au-C(alkyne) σ-bond, conferring carbocationic character (and reactivity) to the distal alkyne C atom.

 

 10.1021/cs5001575

Keywords

Ab initio molecular dynamics Density functional theory Gold catalysis Mesoionic carbene Thermodynamic and kinetic control