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Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis

The merger of photoredox and transition-metal catalysis has evolved as a robust platform in organic synthesis over the past decade. The stereoselective 1,4-functionalization of 1,3-enynes, a prevalent synthon in synthetic chemistry, could afford valuable chiral allene derivatives. However, tremendou...

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Autores principales: Zhang, Feng-Hua, Guo, Xiaochong, Zeng, Xianrong, Wang, Zhaobin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9418150/
https://www.ncbi.nlm.nih.gov/pubmed/36028488
http://dx.doi.org/10.1038/s41467-022-32614-4
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author Zhang, Feng-Hua
Guo, Xiaochong
Zeng, Xianrong
Wang, Zhaobin
author_facet Zhang, Feng-Hua
Guo, Xiaochong
Zeng, Xianrong
Wang, Zhaobin
author_sort Zhang, Feng-Hua
collection PubMed
description The merger of photoredox and transition-metal catalysis has evolved as a robust platform in organic synthesis over the past decade. The stereoselective 1,4-functionalization of 1,3-enynes, a prevalent synthon in synthetic chemistry, could afford valuable chiral allene derivatives. However, tremendous efforts have been focused on the ionic reaction pathway. The radical-involved asymmetric 1,4-functionalization of 1,3-enynes remains a prominent challenge. Herein, we describe the asymmetric three-component 1,4-dialkylation of 1,3-enynes via dual photoredox and chromium catalysis to provide chiral allenols. This method features readily available starting materials, broad substrate scope, good functional group compatibility, high regioselectivity, and simultaneous control of axial and central chiralities. Mechanistic studies suggest that this reaction proceeds through a radical-involved redox-neutral pathway.
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spelling pubmed-94181502022-08-28 Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis Zhang, Feng-Hua Guo, Xiaochong Zeng, Xianrong Wang, Zhaobin Nat Commun Article The merger of photoredox and transition-metal catalysis has evolved as a robust platform in organic synthesis over the past decade. The stereoselective 1,4-functionalization of 1,3-enynes, a prevalent synthon in synthetic chemistry, could afford valuable chiral allene derivatives. However, tremendous efforts have been focused on the ionic reaction pathway. The radical-involved asymmetric 1,4-functionalization of 1,3-enynes remains a prominent challenge. Herein, we describe the asymmetric three-component 1,4-dialkylation of 1,3-enynes via dual photoredox and chromium catalysis to provide chiral allenols. This method features readily available starting materials, broad substrate scope, good functional group compatibility, high regioselectivity, and simultaneous control of axial and central chiralities. Mechanistic studies suggest that this reaction proceeds through a radical-involved redox-neutral pathway. Nature Publishing Group UK 2022-08-26 /pmc/articles/PMC9418150/ /pubmed/36028488 http://dx.doi.org/10.1038/s41467-022-32614-4 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
Zhang, Feng-Hua
Guo, Xiaochong
Zeng, Xianrong
Wang, Zhaobin
Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis
title Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis
title_full Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis
title_fullStr Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis
title_full_unstemmed Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis
title_short Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis
title_sort asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9418150/
https://www.ncbi.nlm.nih.gov/pubmed/36028488
http://dx.doi.org/10.1038/s41467-022-32614-4
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