Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes
Type
ArticleKAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2014-03-27Online Publication Date
2014-03-27Print Publication Date
2014-05-02Permanent link to this record
http://hdl.handle.net/10754/563538
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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. © 2014 American Chemical Society.Citation
Vummaleti, S. V. C., Falivene, L., Poater, A., & Cavallo, L. (2014). Deconstructing Selectivity in the Gold-Promoted Cyclization of Alkynyl Benzothioamides to Six-Membered Mesoionic Carbene or Acyclic Carbene Complexes. ACS Catalysis, 4(5), 1287–1291. doi:10.1021/cs5001575Publisher
American Chemical Society (ACS)Journal
ACS Catalysisae974a485f413a2113503eed53cd6c53
10.1021/cs5001575