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Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis

The intermolecular three-component alkene vicinal dicarbofunctionalization (DCF) reaction allows installation of two different carbon fragments. Despite extensive investigation into its ionic chemistry, the enantioseletive radical-mediated versions of DCF reactions remain largely unexplored. Herein,...

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Autores principales: Wang, Peng-Zi, Gao, Yuan, Chen, Jun, Huan, Xiao-Die, Xiao, Wen-Jing, Chen, Jia-Rong
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7985521/
https://www.ncbi.nlm.nih.gov/pubmed/33753736
http://dx.doi.org/10.1038/s41467-021-22127-x
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author Wang, Peng-Zi
Gao, Yuan
Chen, Jun
Huan, Xiao-Die
Xiao, Wen-Jing
Chen, Jia-Rong
author_facet Wang, Peng-Zi
Gao, Yuan
Chen, Jun
Huan, Xiao-Die
Xiao, Wen-Jing
Chen, Jia-Rong
author_sort Wang, Peng-Zi
collection PubMed
description The intermolecular three-component alkene vicinal dicarbofunctionalization (DCF) reaction allows installation of two different carbon fragments. Despite extensive investigation into its ionic chemistry, the enantioseletive radical-mediated versions of DCF reactions remain largely unexplored. Herein, we report an intermolecular, enantioselective three-component radical vicinal dicarbofunctionalization reaction of olefins enabled by merger of radical addition and cross-coupling using photoredox and copper dual catalysis. Key to the success of this protocol relies on chemoselective addition of acyl and cyanoalkyl radicals, generated in situ from the redox-active oxime esters by a photocatalytic N-centered iminyl radical-triggered C-C bond cleavage event, onto the alkenes to form new carbon radicals. Single electron metalation of such newly formed carbon radicals to TMSCN-derived L1Cu(II)(CN)(2) complex leads to asymmetric cross-coupling. This three-component process proceeds under mild conditions, and tolerates a diverse range of functionalities and synthetic handles, leading to valuable optically active β–cyano ketones and alkyldinitriles, respectively, in a highly enantioselective manner (>60 examples, up to 97% ee).
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spelling pubmed-79855212021-04-16 Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis Wang, Peng-Zi Gao, Yuan Chen, Jun Huan, Xiao-Die Xiao, Wen-Jing Chen, Jia-Rong Nat Commun Article The intermolecular three-component alkene vicinal dicarbofunctionalization (DCF) reaction allows installation of two different carbon fragments. Despite extensive investigation into its ionic chemistry, the enantioseletive radical-mediated versions of DCF reactions remain largely unexplored. Herein, we report an intermolecular, enantioselective three-component radical vicinal dicarbofunctionalization reaction of olefins enabled by merger of radical addition and cross-coupling using photoredox and copper dual catalysis. Key to the success of this protocol relies on chemoselective addition of acyl and cyanoalkyl radicals, generated in situ from the redox-active oxime esters by a photocatalytic N-centered iminyl radical-triggered C-C bond cleavage event, onto the alkenes to form new carbon radicals. Single electron metalation of such newly formed carbon radicals to TMSCN-derived L1Cu(II)(CN)(2) complex leads to asymmetric cross-coupling. This three-component process proceeds under mild conditions, and tolerates a diverse range of functionalities and synthetic handles, leading to valuable optically active β–cyano ketones and alkyldinitriles, respectively, in a highly enantioselective manner (>60 examples, up to 97% ee). Nature Publishing Group UK 2021-03-22 /pmc/articles/PMC7985521/ /pubmed/33753736 http://dx.doi.org/10.1038/s41467-021-22127-x Text en © The Author(s) 2021 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/.
spellingShingle Article
Wang, Peng-Zi
Gao, Yuan
Chen, Jun
Huan, Xiao-Die
Xiao, Wen-Jing
Chen, Jia-Rong
Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis
title Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis
title_full Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis
title_fullStr Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis
title_full_unstemmed Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis
title_short Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis
title_sort asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7985521/
https://www.ncbi.nlm.nih.gov/pubmed/33753736
http://dx.doi.org/10.1038/s41467-021-22127-x
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