title: Gold-catalyzed oxidative coupling of arylsilanes and arenes: origin of selectivity and improved precatalyst.
abstract: The mechanism of gold-catalyzed coupling of arenes with aryltrimethylsilanes has been investigated, employing an improved precatalyst (thtAuBr3) to facilitate kinetic analysis. In combination with linear free-energy relationships, kinetic isotope effects, and stoichiometric experiments, the data support a mechanism involving an Au(I)/Au(III) redox cycle in which sequential electrophilic aromatic substitution of the arylsilane and the arene by Au(III) precedes product-forming reductive elimination and subsequent cycle-closing reoxidation of the metal. Despite the fundamental mechanistic similarities between the two auration events, high selectivity is observed for heterocoupling (C-Si then C-H auration) over homocoupling of either the arylsilane or the arene (C-Si then C-Si, or C-H then C-H auration); this chemoselectivity originates from differences in the product-determining elementary steps of each electrophilic substitution. The turnover-limiting step of the reaction involves associative substitution en route to an arene π-complex. The ramifications of this insight for implementation of the methodology are discussed.
authors.affiliation: School of Chemistry, University of Edinburgh , Joseph Black Building, West Mains Road, Edinburgh EH9 3JJ, U.K.
authors.forename: Liam T
authors.initials: LT
authors.lastname: Ball
authors.forename: Guy C
authors.initials: GC
authors.lastname: Lloyd-Jones
authors.forename: Christopher A
authors.initials: CA
authors.lastname: Russell