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Unlocking a self-catalytic cycle in a copper-catalyzed aerobic oxidative coupling/cyclization reaction
Presented here is a copper-catalyzed, aerobic oxidative C-H/C-H cyclization reaction, which occurs by cleaving the C-H and N-H bonds of 3-phenylindoles. A broad range of 3-phenylindoles can be well tolerated to produce the indole-containing polycyclic aromatic hydrocarbons (PAH) in good to excellent...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Elsevier
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8881718/ https://www.ncbi.nlm.nih.gov/pubmed/35243259 http://dx.doi.org/10.1016/j.isci.2022.103906 |
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author | Liu, Jianming Wang, Xiaopei Wang, Zhiyue Yang, Yan Tang, Qinghu Liu, Hongchi Huang, Hanmin |
author_facet | Liu, Jianming Wang, Xiaopei Wang, Zhiyue Yang, Yan Tang, Qinghu Liu, Hongchi Huang, Hanmin |
author_sort | Liu, Jianming |
collection | PubMed |
description | Presented here is a copper-catalyzed, aerobic oxidative C-H/C-H cyclization reaction, which occurs by cleaving the C-H and N-H bonds of 3-phenylindoles. A broad range of 3-phenylindoles can be well tolerated to produce the indole-containing polycyclic aromatic hydrocarbons (PAH) in good to excellent yields. An evaluation of the reaction mechanism is enabled by the isolation of the di- and tri-indole intermediates, highlighting the role of the substrate for this catalytic reaction. The results of these controlled experiments and kinetic studies provide solid experimental support for a self-catalysis reaction, which has rarely been observed in oxidative C-H activation reactions. Additional mechanistic studies indicate that the substrate for this reaction accelerates by the following mechanism: The substrate combines with the Cu catalyst to transform the less active di-indole intermediate into a tri-indole intermediate. This intermediate is quickly converted into the desired product along with regeneration of the substrate copper complex. |
format | Online Article Text |
id | pubmed-8881718 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | Elsevier |
record_format | MEDLINE/PubMed |
spelling | pubmed-88817182022-03-02 Unlocking a self-catalytic cycle in a copper-catalyzed aerobic oxidative coupling/cyclization reaction Liu, Jianming Wang, Xiaopei Wang, Zhiyue Yang, Yan Tang, Qinghu Liu, Hongchi Huang, Hanmin iScience Article Presented here is a copper-catalyzed, aerobic oxidative C-H/C-H cyclization reaction, which occurs by cleaving the C-H and N-H bonds of 3-phenylindoles. A broad range of 3-phenylindoles can be well tolerated to produce the indole-containing polycyclic aromatic hydrocarbons (PAH) in good to excellent yields. An evaluation of the reaction mechanism is enabled by the isolation of the di- and tri-indole intermediates, highlighting the role of the substrate for this catalytic reaction. The results of these controlled experiments and kinetic studies provide solid experimental support for a self-catalysis reaction, which has rarely been observed in oxidative C-H activation reactions. Additional mechanistic studies indicate that the substrate for this reaction accelerates by the following mechanism: The substrate combines with the Cu catalyst to transform the less active di-indole intermediate into a tri-indole intermediate. This intermediate is quickly converted into the desired product along with regeneration of the substrate copper complex. Elsevier 2022-02-12 /pmc/articles/PMC8881718/ /pubmed/35243259 http://dx.doi.org/10.1016/j.isci.2022.103906 Text en © 2022 The Author(s) https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Article Liu, Jianming Wang, Xiaopei Wang, Zhiyue Yang, Yan Tang, Qinghu Liu, Hongchi Huang, Hanmin Unlocking a self-catalytic cycle in a copper-catalyzed aerobic oxidative coupling/cyclization reaction |
title | Unlocking a self-catalytic cycle in a copper-catalyzed aerobic oxidative coupling/cyclization reaction |
title_full | Unlocking a self-catalytic cycle in a copper-catalyzed aerobic oxidative coupling/cyclization reaction |
title_fullStr | Unlocking a self-catalytic cycle in a copper-catalyzed aerobic oxidative coupling/cyclization reaction |
title_full_unstemmed | Unlocking a self-catalytic cycle in a copper-catalyzed aerobic oxidative coupling/cyclization reaction |
title_short | Unlocking a self-catalytic cycle in a copper-catalyzed aerobic oxidative coupling/cyclization reaction |
title_sort | unlocking a self-catalytic cycle in a copper-catalyzed aerobic oxidative coupling/cyclization reaction |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8881718/ https://www.ncbi.nlm.nih.gov/pubmed/35243259 http://dx.doi.org/10.1016/j.isci.2022.103906 |
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