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Electrocatalytic redox neutral [3 + 2] annulation of N-cyclopropylanilines and alkenes

Although synthetic organic electrochemistry (EC) has advanced significantly, net redox neutral electrosynthesis is quite rare. Two approaches have been employed to achieve this type of electrosynthesis. One relies on turnover of the product by the reactant in a chain mechanism. The other involves bo...

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Autores principales: Wang, Qi, Wang, Qile, Zhang, Yuexiang, Mohamed, Yasmine M., Pacheco, Carlos, Zheng, Nan, Zare, Richard N., Chen, Hao
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179209/
https://www.ncbi.nlm.nih.gov/pubmed/34163863
http://dx.doi.org/10.1039/d0sc05665k
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author Wang, Qi
Wang, Qile
Zhang, Yuexiang
Mohamed, Yasmine M.
Pacheco, Carlos
Zheng, Nan
Zare, Richard N.
Chen, Hao
author_facet Wang, Qi
Wang, Qile
Zhang, Yuexiang
Mohamed, Yasmine M.
Pacheco, Carlos
Zheng, Nan
Zare, Richard N.
Chen, Hao
author_sort Wang, Qi
collection PubMed
description Although synthetic organic electrochemistry (EC) has advanced significantly, net redox neutral electrosynthesis is quite rare. Two approaches have been employed to achieve this type of electrosynthesis. One relies on turnover of the product by the reactant in a chain mechanism. The other involves both oxidation on the anode and reduction on the cathode in which the radical cation or the radical anion of the product has to migrate between two electrodes. Herein, a home-built electrochemistry/mass spectrometry (EC/MS) platform was used to generate an N-cyclopropylaniline radical cation electrochemically and to monitor its reactivity toward alkenes by mass spectrometry (MS), which led to the discovery of a new redox neutral reaction of intermolecular [3 + 2] annulation of N-cyclopropylanilines and alkenes to provide an aniline-substituted 5-membered carbocycle via direct electrolysis (yield up to 81%). A chain mechanism, involving the regeneration of the substrate radical cation and the formation of the neutral product, is shown to be responsible for promoting such a redox neutral annulation reaction, as supported by experimental evidence of EC/MS.
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spelling pubmed-81792092021-06-22 Electrocatalytic redox neutral [3 + 2] annulation of N-cyclopropylanilines and alkenes Wang, Qi Wang, Qile Zhang, Yuexiang Mohamed, Yasmine M. Pacheco, Carlos Zheng, Nan Zare, Richard N. Chen, Hao Chem Sci Chemistry Although synthetic organic electrochemistry (EC) has advanced significantly, net redox neutral electrosynthesis is quite rare. Two approaches have been employed to achieve this type of electrosynthesis. One relies on turnover of the product by the reactant in a chain mechanism. The other involves both oxidation on the anode and reduction on the cathode in which the radical cation or the radical anion of the product has to migrate between two electrodes. Herein, a home-built electrochemistry/mass spectrometry (EC/MS) platform was used to generate an N-cyclopropylaniline radical cation electrochemically and to monitor its reactivity toward alkenes by mass spectrometry (MS), which led to the discovery of a new redox neutral reaction of intermolecular [3 + 2] annulation of N-cyclopropylanilines and alkenes to provide an aniline-substituted 5-membered carbocycle via direct electrolysis (yield up to 81%). A chain mechanism, involving the regeneration of the substrate radical cation and the formation of the neutral product, is shown to be responsible for promoting such a redox neutral annulation reaction, as supported by experimental evidence of EC/MS. The Royal Society of Chemistry 2020-11-09 /pmc/articles/PMC8179209/ /pubmed/34163863 http://dx.doi.org/10.1039/d0sc05665k Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Wang, Qi
Wang, Qile
Zhang, Yuexiang
Mohamed, Yasmine M.
Pacheco, Carlos
Zheng, Nan
Zare, Richard N.
Chen, Hao
Electrocatalytic redox neutral [3 + 2] annulation of N-cyclopropylanilines and alkenes
title Electrocatalytic redox neutral [3 + 2] annulation of N-cyclopropylanilines and alkenes
title_full Electrocatalytic redox neutral [3 + 2] annulation of N-cyclopropylanilines and alkenes
title_fullStr Electrocatalytic redox neutral [3 + 2] annulation of N-cyclopropylanilines and alkenes
title_full_unstemmed Electrocatalytic redox neutral [3 + 2] annulation of N-cyclopropylanilines and alkenes
title_short Electrocatalytic redox neutral [3 + 2] annulation of N-cyclopropylanilines and alkenes
title_sort electrocatalytic redox neutral [3 + 2] annulation of n-cyclopropylanilines and alkenes
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179209/
https://www.ncbi.nlm.nih.gov/pubmed/34163863
http://dx.doi.org/10.1039/d0sc05665k
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