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Pintus, Anna, Rocchigiani, Luca, Fernandez-Cestau, Julio, Budzelaar, Peter H.M. and Bochmann, Manfred 
ORCID: https://orcid.org/0000-0001-7736-5428
(2016)
Stereo- and regioselective alkyne hydrometallation with gold(III) hydrides.
Angewandte Chemie-International Edition, 55 (40).
12321–12324.
ISSN 1433-7851
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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.
| Item Type: | Article |
|---|---|
| Additional Information: | © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. |
| Uncontrolled Keywords: | alkynes,density functional calculations,gold,insertion,reaction mechanisms |
| Faculty \ School: | Faculty of Science > School of Chemistry |
| UEA Research Groups: | Faculty of Science > Research Groups > Synthetic Chemistry (former - to 2017) Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Chemistry of Materials and Catalysis |
| Depositing User: | Pure Connector |
| Date Deposited: | 23 Sep 2016 15:00 |
| Last Modified: | 29 Mar 2024 01:41 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/59696 |
| DOI: | 10.1002/anie.201607522 |
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