Gold-Catalyzed Oxidative Coupling of Arylsilanes and Arenes: Origin of Selectivity and Improved Precatalyst

Liam T. Ball, Guy C. Lloyd-Jones, Christopher A. Russell

Research output: Contribution to journalArticlepeer-review

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 pi-complex. The ramifications of this insight for implementation of the methodology are discussed.

Original languageEnglish
Pages (from-to)254-264
Number of pages11
JournalJournal of the American Chemical Society
Volume136
Issue number1
Early online date24 Dec 2013
DOIs
Publication statusPublished - 8 Jan 2014

Keywords

  • C-H ACTIVATION
  • ELECTROPHILIC AROMATIC-SUBSTITUTION
  • SI-AR BOND
  • REDUCTIVE ELIMINATION
  • RELATIVE REACTIVITIES
  • ORGANOGOLD COMPOUNDS
  • NONACTIVATED ARENES
  • DIRECT ARYLATION
  • BORONIC ACIDS
  • CATIONIC GOLD

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