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Nickel-catalysed selective migratory hydrothiolation of alkenes and alkynes with thiols

Direct (utilize easily available and abundant precursors) and selective (both chemo- and regio-) aliphatic C–H functionalization is an attractive mean with which to streamline chemical synthesis. With many possible sites of reaction, traditional methods often need an adjacent polar directing group n...

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Detalles Bibliográficos
Autores principales: Zhang, Yulong, Xu, Xianfeng, Zhu, Shaolin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6465347/
https://www.ncbi.nlm.nih.gov/pubmed/30988306
http://dx.doi.org/10.1038/s41467-019-09783-w
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author Zhang, Yulong
Xu, Xianfeng
Zhu, Shaolin
author_facet Zhang, Yulong
Xu, Xianfeng
Zhu, Shaolin
author_sort Zhang, Yulong
collection PubMed
description Direct (utilize easily available and abundant precursors) and selective (both chemo- and regio-) aliphatic C–H functionalization is an attractive mean with which to streamline chemical synthesis. With many possible sites of reaction, traditional methods often need an adjacent polar directing group nearby to achieve high regio- and chemoselectivity and are often restricted to a single site of functionalization. Here we report a remote aliphatic C–H thiolation process with predictable and switchable regioselectivity through NiH-catalysed migratory hydrothiolation of two feedstock chemicals (alkenes/alkynes and thiols). This mild reaction avoids the preparation of electrophilic thiolation reagents and is highly selective to thiols over other nucleophilic groups, such as alcohols, acids, amines, and amides. Mechanistic studies show that the reaction occurs through the formation of an RS-Bpin intermediate, and THF as the solvent plays an important role in the regeneration of NiH species.
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spelling pubmed-64653472019-04-17 Nickel-catalysed selective migratory hydrothiolation of alkenes and alkynes with thiols Zhang, Yulong Xu, Xianfeng Zhu, Shaolin Nat Commun Article Direct (utilize easily available and abundant precursors) and selective (both chemo- and regio-) aliphatic C–H functionalization is an attractive mean with which to streamline chemical synthesis. With many possible sites of reaction, traditional methods often need an adjacent polar directing group nearby to achieve high regio- and chemoselectivity and are often restricted to a single site of functionalization. Here we report a remote aliphatic C–H thiolation process with predictable and switchable regioselectivity through NiH-catalysed migratory hydrothiolation of two feedstock chemicals (alkenes/alkynes and thiols). This mild reaction avoids the preparation of electrophilic thiolation reagents and is highly selective to thiols over other nucleophilic groups, such as alcohols, acids, amines, and amides. Mechanistic studies show that the reaction occurs through the formation of an RS-Bpin intermediate, and THF as the solvent plays an important role in the regeneration of NiH species. Nature Publishing Group UK 2019-04-15 /pmc/articles/PMC6465347/ /pubmed/30988306 http://dx.doi.org/10.1038/s41467-019-09783-w Text en © The Author(s) 2019 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
Zhang, Yulong
Xu, Xianfeng
Zhu, Shaolin
Nickel-catalysed selective migratory hydrothiolation of alkenes and alkynes with thiols
title Nickel-catalysed selective migratory hydrothiolation of alkenes and alkynes with thiols
title_full Nickel-catalysed selective migratory hydrothiolation of alkenes and alkynes with thiols
title_fullStr Nickel-catalysed selective migratory hydrothiolation of alkenes and alkynes with thiols
title_full_unstemmed Nickel-catalysed selective migratory hydrothiolation of alkenes and alkynes with thiols
title_short Nickel-catalysed selective migratory hydrothiolation of alkenes and alkynes with thiols
title_sort nickel-catalysed selective migratory hydrothiolation of alkenes and alkynes with thiols
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6465347/
https://www.ncbi.nlm.nih.gov/pubmed/30988306
http://dx.doi.org/10.1038/s41467-019-09783-w
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