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Atropisomerism in Diarylamines: Structural Requirements and Mechanisms of Conformational Interconversion

In common with other hindered structures containing two aromatic rings linked by a short tether, diarylamines may exhibit atropisomerism (chirality due to restricted rotation). Previous examples have principally been tertiary amines, especially those with cyclic scaffolds. Little is known of the str...

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Autores principales: Costil, Romain, Sterling, Alistair J., Duarte, Fernanda, Clayden, Jonathan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7589358/
https://www.ncbi.nlm.nih.gov/pubmed/32633101
http://dx.doi.org/10.1002/anie.202007595
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author Costil, Romain
Sterling, Alistair J.
Duarte, Fernanda
Clayden, Jonathan
author_facet Costil, Romain
Sterling, Alistair J.
Duarte, Fernanda
Clayden, Jonathan
author_sort Costil, Romain
collection PubMed
description In common with other hindered structures containing two aromatic rings linked by a short tether, diarylamines may exhibit atropisomerism (chirality due to restricted rotation). Previous examples have principally been tertiary amines, especially those with cyclic scaffolds. Little is known of the structural requirement for atropisomerism in structurally simpler secondary and acyclic diarylamines. In this paper we describe a systematic study of a series of acyclic secondary diarylamines, and we quantify the degree of steric hindrance in the ortho positions that is required for atropisomerism to result. Through a detailed experimental and computational analysis, the role of each ortho‐substituent on the mechanism and rate of conformational interconversion is rationalised. We also present a simple predictive model for the design of configurationally stable secondary diarylamines.
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spelling pubmed-75893582020-10-30 Atropisomerism in Diarylamines: Structural Requirements and Mechanisms of Conformational Interconversion Costil, Romain Sterling, Alistair J. Duarte, Fernanda Clayden, Jonathan Angew Chem Int Ed Engl Research Articles In common with other hindered structures containing two aromatic rings linked by a short tether, diarylamines may exhibit atropisomerism (chirality due to restricted rotation). Previous examples have principally been tertiary amines, especially those with cyclic scaffolds. Little is known of the structural requirement for atropisomerism in structurally simpler secondary and acyclic diarylamines. In this paper we describe a systematic study of a series of acyclic secondary diarylamines, and we quantify the degree of steric hindrance in the ortho positions that is required for atropisomerism to result. Through a detailed experimental and computational analysis, the role of each ortho‐substituent on the mechanism and rate of conformational interconversion is rationalised. We also present a simple predictive model for the design of configurationally stable secondary diarylamines. John Wiley and Sons Inc. 2020-08-20 2020-10-12 /pmc/articles/PMC7589358/ /pubmed/32633101 http://dx.doi.org/10.1002/anie.202007595 Text en © 2020 The Authors. Published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Research Articles
Costil, Romain
Sterling, Alistair J.
Duarte, Fernanda
Clayden, Jonathan
Atropisomerism in Diarylamines: Structural Requirements and Mechanisms of Conformational Interconversion
title Atropisomerism in Diarylamines: Structural Requirements and Mechanisms of Conformational Interconversion
title_full Atropisomerism in Diarylamines: Structural Requirements and Mechanisms of Conformational Interconversion
title_fullStr Atropisomerism in Diarylamines: Structural Requirements and Mechanisms of Conformational Interconversion
title_full_unstemmed Atropisomerism in Diarylamines: Structural Requirements and Mechanisms of Conformational Interconversion
title_short Atropisomerism in Diarylamines: Structural Requirements and Mechanisms of Conformational Interconversion
title_sort atropisomerism in diarylamines: structural requirements and mechanisms of conformational interconversion
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7589358/
https://www.ncbi.nlm.nih.gov/pubmed/32633101
http://dx.doi.org/10.1002/anie.202007595
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