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

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

Sai Vikrama Chaitanya Vummaleti, Laura Falivene, Albert Poater and Luigi Cavallo
ACS catalysis, Vol.4(5), pp.1287-1291
02/05/2014
DOI: https://doi.org/10.1021/cs5001575

Abstract

Chemistry Chemistry, Physical Physical Sciences Science & Technology
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.

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