Stable gold(III) catalysts by oxidative addition of a carbon–carbon bond

Chung-Yeh Wu, Takahiro Horibe, Christian Borch Jacobsen and F. Dean Toste ()
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Chung-Yeh Wu: University of California
Takahiro Horibe: University of California
Christian Borch Jacobsen: University of California
F. Dean Toste: University of California

Nature, 2015, vol. 517, issue 7535, 449-454

Abstract: Abstract Low-valent late transition-metal catalysis has become indispensable to chemical synthesis, but homogeneous high-valent transition-metal catalysis is underdeveloped, mainly owing to the reactivity of high-valent transition-metal complexes and the challenges associated with synthesizing them. Here we report a carbon–carbon bond cleavage at ambient conditions by a Au(i) complex that generates a stable Au(iii) cationic complex. In contrast to the well-established soft and carbophilic Au(i) catalyst, this Au(iii) complex exhibits hard, oxophilic Lewis acidity. For example, we observed catalytic activation of α,β-unsaturated aldehydes towards selective conjugate additions as well as activation of an unsaturated aldehyde-allene for a [2 + 2] cycloaddition reaction. The origin of the regioselectivity and catalytic activity was elucidated by X-ray crystallographic analysis of an isolated Au(iii)-activated cinnamaldehyde intermediate. The concepts revealed suggest a strategy for accessing high-valent transition-metal catalysis from readily available precursors.

Date: 2015
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DOI: 10.1038/nature14104

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