Stereo‐ and Regioselective Alkyne Hydrometallation with Gold(III) Hydrides |
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| Authors: | Dr. Anna Pintus Dr. Luca Rocchigiani Dr. Julio Fernandez‐Cestau Prof. Dr. Peter H. M. Budzelaar Prof. Dr. Manfred Bochmann |
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| Affiliation: | 1. School of Chemistry, University of East Anglia, Norwich, UK;2. Department of Chemistry, University of Manitoba, Winnipeg, Manitoba, Canada |
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| 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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| Keywords: | alkynes density functional calculations gold insertion reaction mechanisms |
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