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Regiospecific α-methylene functionalisation of tertiary amines with alkynes via Au-catalysed concerted one-proton/two-electron transfer to O(2)
Regioselective transformations of tertiary amines, which are ubiquitously present in natural products and drugs, are important for the development of novel medicines. In particular, the oxidative α-C–H functionalisation of tertiary amines with nucleophiles via iminium cations is a promising approach...
Autores principales: | , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9646731/ https://www.ncbi.nlm.nih.gov/pubmed/36351920 http://dx.doi.org/10.1038/s41467-022-34176-x |
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author | Yatabe, Takafumi Yamaguchi, Kazuya |
author_facet | Yatabe, Takafumi Yamaguchi, Kazuya |
author_sort | Yatabe, Takafumi |
collection | PubMed |
description | Regioselective transformations of tertiary amines, which are ubiquitously present in natural products and drugs, are important for the development of novel medicines. In particular, the oxidative α-C–H functionalisation of tertiary amines with nucleophiles via iminium cations is a promising approach because, theoretically, there is almost no limit to the type of amine and functionalisation. However, most of the reports on oxidative α-C–H functionalisations are limited to α-methyl-selective or non-selective reactions, despite the frequent appearance of α-methylene-substituted amines in pharmaceutical fields. Herein, we develop an unusual oxidative regiospecific α-methylene functionalisation of structurally diverse tertiary amines with alkynes to synthesise various propargylic amines using a catalyst comprising Zn salts and hydroxyapatite-supported Au nanoparticles. Thorough experimental investigations suggest that the unusual α-methylene regiospecificity is probably due to a concerted one-proton/two-electron transfer from amines to O(2) on the Au nanoparticle catalyst, which paves the way to other α-methylene-specific functionalisations. |
format | Online Article Text |
id | pubmed-9646731 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-96467312022-11-15 Regiospecific α-methylene functionalisation of tertiary amines with alkynes via Au-catalysed concerted one-proton/two-electron transfer to O(2) Yatabe, Takafumi Yamaguchi, Kazuya Nat Commun Article Regioselective transformations of tertiary amines, which are ubiquitously present in natural products and drugs, are important for the development of novel medicines. In particular, the oxidative α-C–H functionalisation of tertiary amines with nucleophiles via iminium cations is a promising approach because, theoretically, there is almost no limit to the type of amine and functionalisation. However, most of the reports on oxidative α-C–H functionalisations are limited to α-methyl-selective or non-selective reactions, despite the frequent appearance of α-methylene-substituted amines in pharmaceutical fields. Herein, we develop an unusual oxidative regiospecific α-methylene functionalisation of structurally diverse tertiary amines with alkynes to synthesise various propargylic amines using a catalyst comprising Zn salts and hydroxyapatite-supported Au nanoparticles. Thorough experimental investigations suggest that the unusual α-methylene regiospecificity is probably due to a concerted one-proton/two-electron transfer from amines to O(2) on the Au nanoparticle catalyst, which paves the way to other α-methylene-specific functionalisations. Nature Publishing Group UK 2022-11-09 /pmc/articles/PMC9646731/ /pubmed/36351920 http://dx.doi.org/10.1038/s41467-022-34176-x Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/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/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Yatabe, Takafumi Yamaguchi, Kazuya Regiospecific α-methylene functionalisation of tertiary amines with alkynes via Au-catalysed concerted one-proton/two-electron transfer to O(2) |
title | Regiospecific α-methylene functionalisation of tertiary amines with alkynes via Au-catalysed concerted one-proton/two-electron transfer to O(2) |
title_full | Regiospecific α-methylene functionalisation of tertiary amines with alkynes via Au-catalysed concerted one-proton/two-electron transfer to O(2) |
title_fullStr | Regiospecific α-methylene functionalisation of tertiary amines with alkynes via Au-catalysed concerted one-proton/two-electron transfer to O(2) |
title_full_unstemmed | Regiospecific α-methylene functionalisation of tertiary amines with alkynes via Au-catalysed concerted one-proton/two-electron transfer to O(2) |
title_short | Regiospecific α-methylene functionalisation of tertiary amines with alkynes via Au-catalysed concerted one-proton/two-electron transfer to O(2) |
title_sort | regiospecific α-methylene functionalisation of tertiary amines with alkynes via au-catalysed concerted one-proton/two-electron transfer to o(2) |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9646731/ https://www.ncbi.nlm.nih.gov/pubmed/36351920 http://dx.doi.org/10.1038/s41467-022-34176-x |
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