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

Anna Pintus; Luca Rocchigiani; Julio Fernandez-Cestau; Peter H.M. Budzelaar; Manfred Bochmann

doi:10.1002/anie.201607522

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

Anna Pintus, Luca Rocchigiani, Julio Fernandez-Cestau, Peter H.M. Budzelaar, Manfred Bochmann

Research output: Contribution to journal › Article › peer-review

45 Citations (Scopus)

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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.

Original language	English
Pages (from-to)	12321–12324
Number of pages	4
Journal	Angewandte Chemie-International Edition
Volume	55
Issue number	40
Early online date	4 Sep 2016
DOIs	https://doi.org/10.1002/anie.201607522 https://doi.org/10.1002/ange.201607522
Publication status	Published - 26 Sep 2016

Keywords

alkynes
density functional calculations
gold
insertion
reaction mechanisms

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10.1002/anie.201607522Licence: CC BY-NC
10.1002/ange.201607522Licence: CC BY-NC

ACIE 2016, 55, 12321Final published version, 733 KBLicence: CC BY-NC

Manfred Bochmann
- M.Bochmannuea.acuk
- School of Chemistry, Pharmacy and Pharmacology - Emeritus Professor
- Chemistry of Light and Energy - Member
- Chemistry of Materials and Catalysis - Member
Person: Honorary, Research Group Member

Gold(III) Chemistry: Structures, Bonding, Reactivity and Catalysis
Bochmann, M.
CEC (Framework 7)
1/02/14 → 31/01/19
Project: Research

Cite this

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title = "Stereo- and regioselective alkyne hydrometallation with gold(III) hydrides",

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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AU - Pintus, Anna

AU - Rocchigiani, Luca

AU - Fernandez-Cestau, Julio

AU - Budzelaar, Peter H.M.

AU - Bochmann, Manfred

N1 - © 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.

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N2 - 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.

AB - 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.

KW - alkynes

KW - density functional calculations

KW - gold

KW - insertion

KW - reaction mechanisms

U2 - 10.1002/anie.201607522

DO - 10.1002/anie.201607522

M3 - Article

VL - 55

SP - 12321

EP - 12324

JO - Angewandte Chemie-International Edition

JF - Angewandte Chemie-International Edition

SN - 1433-7851

IS - 40

ER -

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

Abstract

Keywords

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Profiles

Manfred Bochmann

Projects

Gold(III) Chemistry: Structures, Bonding, Reactivity and Catalysis

Cite this