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Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands

A wide range of Cu(II)-catalyzed C–H activation reactions have been realized since 2006, however, whether a C–H metalation mechanism similar to Pd(II)-catalyzed C–H activation reaction is operating remains an open question. To address this question and ultimately develop ligand accelerated Cu(II)-ca...

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Autores principales: Kuang, Xin, Li, Jian-Jun, Liu, Tao, Ding, Chang-Hua, Wu, Kevin, Wang, Peng, Yu, Jin-Quan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10673954/
https://www.ncbi.nlm.nih.gov/pubmed/38001060
http://dx.doi.org/10.1038/s41467-023-43278-z
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author Kuang, Xin
Li, Jian-Jun
Liu, Tao
Ding, Chang-Hua
Wu, Kevin
Wang, Peng
Yu, Jin-Quan
author_facet Kuang, Xin
Li, Jian-Jun
Liu, Tao
Ding, Chang-Hua
Wu, Kevin
Wang, Peng
Yu, Jin-Quan
author_sort Kuang, Xin
collection PubMed
description A wide range of Cu(II)-catalyzed C–H activation reactions have been realized since 2006, however, whether a C–H metalation mechanism similar to Pd(II)-catalyzed C–H activation reaction is operating remains an open question. To address this question and ultimately develop ligand accelerated Cu(II)-catalyzed C–H activation reactions, realizing the enantioselective version and investigating the mechanism is critically important. With a modified chiral BINOL ligand, we report the first example of Cu-mediated enantioselective C–H activation reaction for the construction of planar chiral ferrocenes with high yields and stereoinduction. The key to the success of this reaction is the discovery of a ligand acceleration effect with the BINOL-based diol ligand in the directed Cu-catalyzed C–H alkynylation of ferrocene derivatives bearing an oxazoline-aniline directing group. This transformation is compatible with terminal aryl and alkyl alkynes, which are incompatible with Pd-catalyzed C–H activation reactions. This finding provides an invaluable mechanistic information in determining whether Cu(II) cleaves C–H bonds via CMD pathway in analogous manner to Pd(II) catalysts.
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spelling pubmed-106739542023-11-24 Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands Kuang, Xin Li, Jian-Jun Liu, Tao Ding, Chang-Hua Wu, Kevin Wang, Peng Yu, Jin-Quan Nat Commun Article A wide range of Cu(II)-catalyzed C–H activation reactions have been realized since 2006, however, whether a C–H metalation mechanism similar to Pd(II)-catalyzed C–H activation reaction is operating remains an open question. To address this question and ultimately develop ligand accelerated Cu(II)-catalyzed C–H activation reactions, realizing the enantioselective version and investigating the mechanism is critically important. With a modified chiral BINOL ligand, we report the first example of Cu-mediated enantioselective C–H activation reaction for the construction of planar chiral ferrocenes with high yields and stereoinduction. The key to the success of this reaction is the discovery of a ligand acceleration effect with the BINOL-based diol ligand in the directed Cu-catalyzed C–H alkynylation of ferrocene derivatives bearing an oxazoline-aniline directing group. This transformation is compatible with terminal aryl and alkyl alkynes, which are incompatible with Pd-catalyzed C–H activation reactions. This finding provides an invaluable mechanistic information in determining whether Cu(II) cleaves C–H bonds via CMD pathway in analogous manner to Pd(II) catalysts. Nature Publishing Group UK 2023-11-24 /pmc/articles/PMC10673954/ /pubmed/38001060 http://dx.doi.org/10.1038/s41467-023-43278-z Text en © The Author(s) 2023 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 licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence 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 licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Kuang, Xin
Li, Jian-Jun
Liu, Tao
Ding, Chang-Hua
Wu, Kevin
Wang, Peng
Yu, Jin-Quan
Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands
title Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands
title_full Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands
title_fullStr Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands
title_full_unstemmed Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands
title_short Cu-mediated enantioselective C–H alkynylation of ferrocenes with chiral BINOL ligands
title_sort cu-mediated enantioselective c–h alkynylation of ferrocenes with chiral binol ligands
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10673954/
https://www.ncbi.nlm.nih.gov/pubmed/38001060
http://dx.doi.org/10.1038/s41467-023-43278-z
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