Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: turnover-limiting reductive elimination versus π-complexation
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 a...
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American Chemical Society
2016
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| Online Access: | https://eprints.nottingham.ac.uk/39698/ |
| _version_ | 1848795894090039296 |
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| author | Corrie, Tom J.A. Ball, Liam T. Russell, Christopher A. Lloyd-Jones, Guy C. |
| author_facet | Corrie, Tom J.A. Ball, Liam T. Russell, Christopher A. Lloyd-Jones, Guy C. |
| author_sort | Corrie, Tom J.A. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T19:39:20Z |
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| id | nottingham-39698 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:39:20Z |
| publishDate | 2016 |
| publisher | American Chemical Society |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-396982020-05-04T18:26:28Z https://eprints.nottingham.ac.uk/39698/ Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: turnover-limiting reductive elimination versus π-complexation Corrie, Tom J.A. Ball, Liam T. Russell, Christopher A. Lloyd-Jones, Guy C. 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. American Chemical Society 2016-12-12 Article PeerReviewed Corrie, Tom J.A., Ball, Liam T., Russell, Christopher A. and Lloyd-Jones, Guy C. (2016) Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: turnover-limiting reductive elimination versus π-complexation. Journal of the American Chemical Society . ISSN 1520-5126 http://pubs.acs.org/doi/abs/10.1021/jacs.6b10018 doi:10.1021/jacs.6b10018 doi:10.1021/jacs.6b10018 |
| spellingShingle | 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 π-complexation |
| title | Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: turnover-limiting reductive elimination versus π-complexation |
| title_full | Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: turnover-limiting reductive elimination versus π-complexation |
| title_fullStr | Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: turnover-limiting reductive elimination versus π-complexation |
| title_full_unstemmed | Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: turnover-limiting reductive elimination versus π-complexation |
| title_short | Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: turnover-limiting reductive elimination versus π-complexation |
| title_sort | au-catalyzed biaryl coupling to generate 5- to 9-membered rings: turnover-limiting reductive elimination versus π-complexation |
| url | https://eprints.nottingham.ac.uk/39698/ https://eprints.nottingham.ac.uk/39698/ https://eprints.nottingham.ac.uk/39698/ |