Projects per year
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.
Original language | English |
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Pages (from-to) | 254-264 |
Number of pages | 11 |
Journal | Journal of the American Chemical Society |
Volume | 136 |
Issue number | 1 |
Early online date | 24 Dec 2013 |
DOIs | |
Publication status | Published - 8 Jan 2014 |
Research Groups and Themes
- BCS and TECS CDTs
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Dive into the research topics of 'Gold-catalyzed oxidative coupling of arylsilanes and arenes: Origin of selectivity and improved precatalyst'. Together they form a unique fingerprint.Projects
- 1 Finished
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3-month Core Capability for Chemistry Research
Crosby, J. (Principal Investigator)
1/01/13 → 1/04/13
Project: Research