Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 136, Issue 1, Pages 254-264Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja408712e
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Funding
- Bristol Chemical Synthesis CDT (EPSRC) [EP/G036764/1]
- EPSRC [EP/K03927X/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/K03927X/1] Funding Source: researchfish
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The mechanism of gold-catalyzed coupling of arenes with aryltrimethylsilanes has been investigated, employing an improved precatalyst (thtAuBr(3)) 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.
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