Synthesis of highly substituted alkenes by sulfur-mediated olefination of N-tosylhydrazones
Tetraphenylethylenes (TPEs) are well-known for their aggregation-induced emission properties. The synthesis of TPE derivatives, as well as other highly substituted olefins, generally requires the use of hazardous reagents, such as metalorganic compounds, to overcome the high activation energies caus...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10657425/ https://www.ncbi.nlm.nih.gov/pubmed/37980378 http://dx.doi.org/10.1038/s42004-023-01058-2 |
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author | Conen, Peter Nickisch, Roman Meier, Michael A. R. |
author_facet | Conen, Peter Nickisch, Roman Meier, Michael A. R. |
author_sort | Conen, Peter |
collection | PubMed |
description | Tetraphenylethylenes (TPEs) are well-known for their aggregation-induced emission properties. The synthesis of TPE derivatives, as well as other highly substituted olefins, generally requires the use of hazardous reagents, such as metalorganic compounds, to overcome the high activation energies caused by the sterically congested double bond. Herein, we present an efficient and metal-free procedure for the synthesis of tetraarylethylenes via alkylidene-homocoupling of N-tosylhydrazones, derived from readily available benzophenones, in excellent yields. The method relies only on cheap and benign additives, i.e. elemental sulfur and potassium carbonate, and easily competes with other established procedures in terms of scope, yield and practicability. A mechanistic study revealed a diazo compound, a thioketone and a thiirane as key intermediates in the pathway of the reaction. Based on this, a modified method, which allows for selective alkylidene-cross-coupling, generating a broader scope of tri- and tetrasubstituted olefins in good yields, is showcased as well. |
format | Online Article Text |
id | pubmed-10657425 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-106574252023-11-18 Synthesis of highly substituted alkenes by sulfur-mediated olefination of N-tosylhydrazones Conen, Peter Nickisch, Roman Meier, Michael A. R. Commun Chem Article Tetraphenylethylenes (TPEs) are well-known for their aggregation-induced emission properties. The synthesis of TPE derivatives, as well as other highly substituted olefins, generally requires the use of hazardous reagents, such as metalorganic compounds, to overcome the high activation energies caused by the sterically congested double bond. Herein, we present an efficient and metal-free procedure for the synthesis of tetraarylethylenes via alkylidene-homocoupling of N-tosylhydrazones, derived from readily available benzophenones, in excellent yields. The method relies only on cheap and benign additives, i.e. elemental sulfur and potassium carbonate, and easily competes with other established procedures in terms of scope, yield and practicability. A mechanistic study revealed a diazo compound, a thioketone and a thiirane as key intermediates in the pathway of the reaction. Based on this, a modified method, which allows for selective alkylidene-cross-coupling, generating a broader scope of tri- and tetrasubstituted olefins in good yields, is showcased as well. Nature Publishing Group UK 2023-11-18 /pmc/articles/PMC10657425/ /pubmed/37980378 http://dx.doi.org/10.1038/s42004-023-01058-2 Text en © The Author(s) 2023 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 licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence 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 licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Conen, Peter Nickisch, Roman Meier, Michael A. R. Synthesis of highly substituted alkenes by sulfur-mediated olefination of N-tosylhydrazones |
title | Synthesis of highly substituted alkenes by sulfur-mediated olefination of N-tosylhydrazones |
title_full | Synthesis of highly substituted alkenes by sulfur-mediated olefination of N-tosylhydrazones |
title_fullStr | Synthesis of highly substituted alkenes by sulfur-mediated olefination of N-tosylhydrazones |
title_full_unstemmed | Synthesis of highly substituted alkenes by sulfur-mediated olefination of N-tosylhydrazones |
title_short | Synthesis of highly substituted alkenes by sulfur-mediated olefination of N-tosylhydrazones |
title_sort | synthesis of highly substituted alkenes by sulfur-mediated olefination of n-tosylhydrazones |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10657425/ https://www.ncbi.nlm.nih.gov/pubmed/37980378 http://dx.doi.org/10.1038/s42004-023-01058-2 |
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