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- Title
Stereo- and Regioselective Alkyne Hydrometallation with Gold(III) Hydrides.
- Authors
Pintus, Anna; Rocchigiani, Luca; Fernandez-Cestau, Julio; Budzelaar, Peter H. M.; Bochmann, Manfred
- 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.
- Subjects
REGIOSELECTIVITY (Chemistry); STEREOCHEMISTRY; GOLD hydride; AZOBISISOBUTYRONITRILE; DENSITY functional theory
- Publication
Angewandte Chemie International Edition, 2016, Vol 55, Issue 40, p12321
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201607522