Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes
KAUST DepartmentKAUST Catalysis Center (KCC)
Physical Sciences and Engineering (PSE) Division
Chemical Science Program
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AbstractWe 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.
PublisherAmerican Chemical Society (ACS)