The hydroauration of internal and terminal alkynes by gold(III) hydride complexes [(C^N^C)AuH] was found to be mediated by radicals and proceeds by an unexpected binuclear outer-sphere mechanism to cleanly form trans-insertion products. Radical precursors such as azobisisobutyronitrile lead to a drastic rate enhancement. DFT calculations support the proposed radical mechanism, with very low activation barriers, and rule out mononuclear mechanistic alternatives. These alkyne hydroaurations are highly regio- and stereospecific for the formation of Z-vinyl isomers, with Z/E ratios of >99:1 in most cases.

Stereo- and Regioselective Alkyne Hydrometallation with Gold(III) Hydrides

Rocchigiani L.;
2016

Abstract

The hydroauration of internal and terminal alkynes by gold(III) hydride complexes [(C^N^C)AuH] was found to be mediated by radicals and proceeds by an unexpected binuclear outer-sphere mechanism to cleanly form trans-insertion products. Radical precursors such as azobisisobutyronitrile lead to a drastic rate enhancement. DFT calculations support the proposed radical mechanism, with very low activation barriers, and rule out mononuclear mechanistic alternatives. These alkyne hydroaurations are highly regio- and stereospecific for the formation of Z-vinyl isomers, with Z/E ratios of >99:1 in most cases.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11391/1534158
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