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

作者：Vummaleti Sai Vikrama Chaitanya; Falivene Laura; Poater Albert; Cavallo Luigi^*

来源：ACS Catalysis, 2014, 4(5): 1287-1291.

DOI：10.1021/cs5001575

• gold catalysis
• mesoionic carbene
• density functional theory
• thermodynamic and kinetic control
• ab initio molecular dynamics

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 Au-III complexes, is connected to a switch from thermodynamic to kinetic reaction control. The Au-III center pushes alkyne coordination toward a single Au-C(alkyne) (sigma-bond, conferring carbocationic character (and reactivity) to the distal alkyne C atom.

• 出版日期2014-5
• 单位KAUST