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...

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Autores principales: Conen, Peter, Nickisch, Roman, Meier, Michael A. R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
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.
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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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