Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes

Sai V. C. Vummaleti; Laura Falivene; Albert Poater; Luigi Cavallo

doi:10.1021/cs5001575

Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes

Sai V. C. Vummaleti, Laura Falivene, Albert Poater, Luigi Cavallo

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

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. © 2014 American Chemical Society.

Original language	English (US)
Pages (from-to)	1287-1291
Number of pages	5
Journal	ACS Catalysis
Volume	4
Issue number	5
DOIs	https://doi.org/10.1021/cs5001575
State	Published - Mar 27 2014

ASJC Scopus subject areas

Catalysis

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title = "Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes",

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. {\textcopyright} 2014 American Chemical Society.",

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AU - Vummaleti, Sai V. C.

AU - Falivene, Laura

AU - Poater, Albert

AU - Cavallo, Luigi

N1 - KAUST Repository Item: Exported on 2020-10-01

PY - 2014/3/27

Y1 - 2014/3/27

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/563538

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UR - http://www.scopus.com/inward/record.url?scp=84899882011&partnerID=8YFLogxK

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Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes

Abstract

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