Stereo- and regioselective alkyne hydrometallation with gold(III) hydrides

Pintus, Anna, Rocchigiani, Luca, Fernandez-Cestau, Julio, Budzelaar, Peter H.M. and Bochmann, Manfred ORCID: (2016) Stereo- and regioselective alkyne hydrometallation with gold(III) hydrides. Angewandte Chemie-International Edition, 55 (40). 12321–12324. ISSN 1433-7851

[thumbnail of ACIE 2016, 55, 12321]
PDF (ACIE 2016, 55, 12321) - Published Version
Available under License Creative Commons Attribution Non-commercial.

Download (750kB) | Preview


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
DOI: 10.1002/anie.201607522


Downloads per month over past year

Actions (login required)

View Item View Item