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Intermolecular diastereoselective annulation of azaarenes into fused N-heterocycles by Ru(II) reductive catalysis

Derivatization of azaarenes can create molecules of biological importance, but reductive functionalization of weakly reactive azaarenes remains a challenge. Here the authors show a dearomative, diastereoselective annulation of azaarenes, via ruthenium(II) reductive catalysis, proceeding with excelle...

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Autores principales: Zhao, He, Wu, Yang, Ci, Chenggang, Tan, Zhenda, Yang, Jian, Jiang, Huanfeng, Dixneuf, Pierre H., Zhang, Min
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9061824/
https://www.ncbi.nlm.nih.gov/pubmed/35501354
http://dx.doi.org/10.1038/s41467-022-29985-z
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author Zhao, He
Wu, Yang
Ci, Chenggang
Tan, Zhenda
Yang, Jian
Jiang, Huanfeng
Dixneuf, Pierre H.
Zhang, Min
author_facet Zhao, He
Wu, Yang
Ci, Chenggang
Tan, Zhenda
Yang, Jian
Jiang, Huanfeng
Dixneuf, Pierre H.
Zhang, Min
author_sort Zhao, He
collection PubMed
description Derivatization of azaarenes can create molecules of biological importance, but reductive functionalization of weakly reactive azaarenes remains a challenge. Here the authors show a dearomative, diastereoselective annulation of azaarenes, via ruthenium(II) reductive catalysis, proceeding with excellent selectivity, mild conditions, and broad substrate and functional group compatibility. Mechanistic studies reveal that the products are formed via hydride transfer-initiated β-aminomethylation and α-arylation of the pyridyl core in the azaarenes, and that paraformaldehyde serves as both the C1-building block and reductant precursor, and the use of Mg(OMe)(2) base plays a critical role in determining the reaction chemo-selectivity by lowering the hydrogen transfer rate. The present work opens a door to further develop valuable reductive functionalization of unsaturated systems by taking profit of formaldehyde-endowed two functions.
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spelling pubmed-90618242022-05-04 Intermolecular diastereoselective annulation of azaarenes into fused N-heterocycles by Ru(II) reductive catalysis Zhao, He Wu, Yang Ci, Chenggang Tan, Zhenda Yang, Jian Jiang, Huanfeng Dixneuf, Pierre H. Zhang, Min Nat Commun Article Derivatization of azaarenes can create molecules of biological importance, but reductive functionalization of weakly reactive azaarenes remains a challenge. Here the authors show a dearomative, diastereoselective annulation of azaarenes, via ruthenium(II) reductive catalysis, proceeding with excellent selectivity, mild conditions, and broad substrate and functional group compatibility. Mechanistic studies reveal that the products are formed via hydride transfer-initiated β-aminomethylation and α-arylation of the pyridyl core in the azaarenes, and that paraformaldehyde serves as both the C1-building block and reductant precursor, and the use of Mg(OMe)(2) base plays a critical role in determining the reaction chemo-selectivity by lowering the hydrogen transfer rate. The present work opens a door to further develop valuable reductive functionalization of unsaturated systems by taking profit of formaldehyde-endowed two functions. Nature Publishing Group UK 2022-05-02 /pmc/articles/PMC9061824/ /pubmed/35501354 http://dx.doi.org/10.1038/s41467-022-29985-z 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
Zhao, He
Wu, Yang
Ci, Chenggang
Tan, Zhenda
Yang, Jian
Jiang, Huanfeng
Dixneuf, Pierre H.
Zhang, Min
Intermolecular diastereoselective annulation of azaarenes into fused N-heterocycles by Ru(II) reductive catalysis
title Intermolecular diastereoselective annulation of azaarenes into fused N-heterocycles by Ru(II) reductive catalysis
title_full Intermolecular diastereoselective annulation of azaarenes into fused N-heterocycles by Ru(II) reductive catalysis
title_fullStr Intermolecular diastereoselective annulation of azaarenes into fused N-heterocycles by Ru(II) reductive catalysis
title_full_unstemmed Intermolecular diastereoselective annulation of azaarenes into fused N-heterocycles by Ru(II) reductive catalysis
title_short Intermolecular diastereoselective annulation of azaarenes into fused N-heterocycles by Ru(II) reductive catalysis
title_sort intermolecular diastereoselective annulation of azaarenes into fused n-heterocycles by ru(ii) reductive catalysis
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9061824/
https://www.ncbi.nlm.nih.gov/pubmed/35501354
http://dx.doi.org/10.1038/s41467-022-29985-z
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