Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 55, Issue 40, Pages 12321-12324Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201607522
Keywords
alkynes; density functional calculations; gold; insertion; reaction mechanisms
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Funding
- European Research Council
- ERC [338944-GOCAT]
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The hydroauration of internal and terminal alkynes by gold(III) hydride complexes [((CNC)-N-boolean AND-C-boolean AND)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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