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Au-Catalyzed Biaryl Coupling To Generate 5- to 9-Membered Rings: Turnover-Limiting Reductive Elimination versus ?-Complexation

Corrie, Tom J.A.; Ball, Liam T.; Russell, Christopher A.; Lloyd-Jones, Guy C.

Au-Catalyzed Biaryl Coupling To Generate 5- to 9-Membered Rings: Turnover-Limiting Reductive Elimination versus ?-Complexation Thumbnail


Authors

Tom J.A. Corrie

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LIAM BALL Liam.Ball@nottingham.ac.uk
Associate Professor

Christopher A. Russell

Guy C. Lloyd-Jones



Abstract

The intramolecular gold–catalyzed arylation of arenes by aryltrimethylsilanes has been investigated from both a mechanistic and preparative aspect. The reaction generates five to nine membered rings, and of the 44 examples studied, ten include a heteroatom (N, O). The tethering of the arene to the arylsilane not only provides a tool to probe the impact of the conforma-tional flexibility of Ar–Au–Ar intermediates, via systematic modulation of the length of aryl-aryl linkage, but also the ability to arylate neutral and electron-poor arenes - substrates that do not react at all in the intermolecular process. Rendering the arylation intramolecular also results in phenomenologically simpler reaction kinetics, and overall these features have facili-tated a detailed study of linear free energy relationships, kinetic isotope effects, and the first quantitative experimental data on the effects of aryl electron-demand and conformational freedom on the rate of reductive elimination from diaryl gold(III) species. The turnover-limiting step for the formation of a series of fluorene derivatives is sensitive to the electronics of the arene and changes from reductive elimination to π-complexation for arenes bearing strongly electron-withdrawing substitu-ents (σ >0.43). Reductive elimination is accelerated by electron-donating substituents (□ = -2.0) on one or both rings, with the individual σ-values being additive in nature. Longer and more flexible tethers between the two aryl rings results in faster reductive elimination from Ar-Au(X)-Ar, and to the π-complexation of the arene by Ar-AuX2 becoming the turnover-limiting step.

Citation

Corrie, T. J., Ball, L. T., Russell, C. A., & Lloyd-Jones, G. C. (2017). Au-Catalyzed Biaryl Coupling To Generate 5- to 9-Membered Rings: Turnover-Limiting Reductive Elimination versus ?-Complexation. Journal of the American Chemical Society, 139(1), 245-254. https://doi.org/10.1021/jacs.6b10018

Journal Article Type Article
Acceptance Date Dec 12, 2016
Online Publication Date Dec 29, 2016
Publication Date Jan 11, 2017
Deposit Date Jan 9, 2017
Publicly Available Date Mar 28, 2024
Journal Journal of the American Chemical Society
Print ISSN 0002-7863
Electronic ISSN 1520-5126
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 139
Issue 1
Pages 245-254
DOI https://doi.org/10.1021/jacs.6b10018
Public URL https://nottingham-repository.worktribe.com/output/835537
Publisher URL http://pubs.acs.org/doi/abs/10.1021/jacs.6b10018

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