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Cleavage of non-polar C(sp(2))‒C(sp(2)) bonds in cycloparaphenylenes via electric field-catalyzed electrophilic aromatic substitution

Electrophilic aromatic substitution (EAS) is one of the most fundamental reactions in organic chemistry. Using an oriented external electric field (OEEF) instead of traditional reagents to tune the EAS reactivity can offer an environmentally friendly method to synthesize aromatic compounds and hold...

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Autores principales: Lin, Junfeng, Lv, Yaxin, Song, Kai, Song, Xuwei, Zang, Hongjun, Du, Pingwu, Zang, Yaping, Zhu, Daoben
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9849230/
https://www.ncbi.nlm.nih.gov/pubmed/36653339
http://dx.doi.org/10.1038/s41467-022-35686-4
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author Lin, Junfeng
Lv, Yaxin
Song, Kai
Song, Xuwei
Zang, Hongjun
Du, Pingwu
Zang, Yaping
Zhu, Daoben
author_facet Lin, Junfeng
Lv, Yaxin
Song, Kai
Song, Xuwei
Zang, Hongjun
Du, Pingwu
Zang, Yaping
Zhu, Daoben
author_sort Lin, Junfeng
collection PubMed
description Electrophilic aromatic substitution (EAS) is one of the most fundamental reactions in organic chemistry. Using an oriented external electric field (OEEF) instead of traditional reagents to tune the EAS reactivity can offer an environmentally friendly method to synthesize aromatic compounds and hold the promise of broadening its scope. Despite these advantages, OEEF catalysis of EAS is difficult to realize, due to the challenge of microscopically orienting OEEF along the direction of electron reorganizations. In this work, we demonstrate OEEF-catalyzed EAS reactions in a series of cycloparaphenylenes (CPPs) using the scanning tunneling microscope break junction (STM-BJ) technique. Crucially, the unique radial π-conjugation of CPPs enables a desired alignment for the OEEF to catalyze the EAS with Au STM tip (or substrate) acting as an electrophile. Under mild conditions, the OEEF-catalyzed EAS reactions can cleave the inherently inert C(sp(2))-C(sp(2)) bond, leading to high-yield (~97%) formation of linear oligophenylenes terminated with covalent Au-C bonds. These results not only demonstrate the feasibility of OEEF catalysis of EAS, but also offer a way of exploring new mechanistic principles of classic organic reactions aided by OEEF.
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spelling pubmed-98492302023-01-20 Cleavage of non-polar C(sp(2))‒C(sp(2)) bonds in cycloparaphenylenes via electric field-catalyzed electrophilic aromatic substitution Lin, Junfeng Lv, Yaxin Song, Kai Song, Xuwei Zang, Hongjun Du, Pingwu Zang, Yaping Zhu, Daoben Nat Commun Article Electrophilic aromatic substitution (EAS) is one of the most fundamental reactions in organic chemistry. Using an oriented external electric field (OEEF) instead of traditional reagents to tune the EAS reactivity can offer an environmentally friendly method to synthesize aromatic compounds and hold the promise of broadening its scope. Despite these advantages, OEEF catalysis of EAS is difficult to realize, due to the challenge of microscopically orienting OEEF along the direction of electron reorganizations. In this work, we demonstrate OEEF-catalyzed EAS reactions in a series of cycloparaphenylenes (CPPs) using the scanning tunneling microscope break junction (STM-BJ) technique. Crucially, the unique radial π-conjugation of CPPs enables a desired alignment for the OEEF to catalyze the EAS with Au STM tip (or substrate) acting as an electrophile. Under mild conditions, the OEEF-catalyzed EAS reactions can cleave the inherently inert C(sp(2))-C(sp(2)) bond, leading to high-yield (~97%) formation of linear oligophenylenes terminated with covalent Au-C bonds. These results not only demonstrate the feasibility of OEEF catalysis of EAS, but also offer a way of exploring new mechanistic principles of classic organic reactions aided by OEEF. Nature Publishing Group UK 2023-01-18 /pmc/articles/PMC9849230/ /pubmed/36653339 http://dx.doi.org/10.1038/s41467-022-35686-4 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
Lin, Junfeng
Lv, Yaxin
Song, Kai
Song, Xuwei
Zang, Hongjun
Du, Pingwu
Zang, Yaping
Zhu, Daoben
Cleavage of non-polar C(sp(2))‒C(sp(2)) bonds in cycloparaphenylenes via electric field-catalyzed electrophilic aromatic substitution
title Cleavage of non-polar C(sp(2))‒C(sp(2)) bonds in cycloparaphenylenes via electric field-catalyzed electrophilic aromatic substitution
title_full Cleavage of non-polar C(sp(2))‒C(sp(2)) bonds in cycloparaphenylenes via electric field-catalyzed electrophilic aromatic substitution
title_fullStr Cleavage of non-polar C(sp(2))‒C(sp(2)) bonds in cycloparaphenylenes via electric field-catalyzed electrophilic aromatic substitution
title_full_unstemmed Cleavage of non-polar C(sp(2))‒C(sp(2)) bonds in cycloparaphenylenes via electric field-catalyzed electrophilic aromatic substitution
title_short Cleavage of non-polar C(sp(2))‒C(sp(2)) bonds in cycloparaphenylenes via electric field-catalyzed electrophilic aromatic substitution
title_sort cleavage of non-polar c(sp(2))‒c(sp(2)) bonds in cycloparaphenylenes via electric field-catalyzed electrophilic aromatic substitution
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9849230/
https://www.ncbi.nlm.nih.gov/pubmed/36653339
http://dx.doi.org/10.1038/s41467-022-35686-4
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