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Ketones from aldehydes via alkyl C(sp(3))−H functionalization under photoredox cooperative NHC/palladium catalysis

Direct synthesis of ketones from aldehydes features high atom- and step-economy. Yet, the coupling of aldehydes with unactivated alkyl C(sp(3))-H remains challenging. Herein, we develop the synthesis of ketones from aldehydes via alkyl C(sp(3))-H functionalization under photoredox cooperative NHC/Pd...

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Autores principales: Wang, Hai-Ying, Wang, Xin-Han, Zhou, Bang-An, Zhang, Chun-Lin, Ye, Song
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10329650/
https://www.ncbi.nlm.nih.gov/pubmed/37422483
http://dx.doi.org/10.1038/s41467-023-39707-8
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author Wang, Hai-Ying
Wang, Xin-Han
Zhou, Bang-An
Zhang, Chun-Lin
Ye, Song
author_facet Wang, Hai-Ying
Wang, Xin-Han
Zhou, Bang-An
Zhang, Chun-Lin
Ye, Song
author_sort Wang, Hai-Ying
collection PubMed
description Direct synthesis of ketones from aldehydes features high atom- and step-economy. Yet, the coupling of aldehydes with unactivated alkyl C(sp(3))-H remains challenging. Herein, we develop the synthesis of ketones from aldehydes via alkyl C(sp(3))-H functionalization under photoredox cooperative NHC/Pd catalysis. The two-component reaction of iodomethylsilyl alkyl ether with aldehydes gave a variety of β-, γ- and δ-silyloxylketones via 1,n-HAT (n = 5, 6, 7) of silylmethyl radicals to generate secondary or tertiary alkyl radicals and following coupling with ketyl radicals from aldehydes under photoredox NHC catalysis. The three-component reaction with the addition of styrenes gave the corresponding ε-hydroxylketones via the generation of benzylic radicals by the addition of alkyl radicals to styrenes and following coupling with ketyl radicals. This work demonstrates the generation of ketyl radical and alkyl radical under the photoredox cooperative NHC/Pd catalysis, and provides two and three component reactions for the synthesis of ketones from aldehydes with alkyl C(sp(3))-H functionalization. The synthetic potential of this protocol was also further illustrated by the late-stage functionalization of natural products.
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spelling pubmed-103296502023-07-10 Ketones from aldehydes via alkyl C(sp(3))−H functionalization under photoredox cooperative NHC/palladium catalysis Wang, Hai-Ying Wang, Xin-Han Zhou, Bang-An Zhang, Chun-Lin Ye, Song Nat Commun Article Direct synthesis of ketones from aldehydes features high atom- and step-economy. Yet, the coupling of aldehydes with unactivated alkyl C(sp(3))-H remains challenging. Herein, we develop the synthesis of ketones from aldehydes via alkyl C(sp(3))-H functionalization under photoredox cooperative NHC/Pd catalysis. The two-component reaction of iodomethylsilyl alkyl ether with aldehydes gave a variety of β-, γ- and δ-silyloxylketones via 1,n-HAT (n = 5, 6, 7) of silylmethyl radicals to generate secondary or tertiary alkyl radicals and following coupling with ketyl radicals from aldehydes under photoredox NHC catalysis. The three-component reaction with the addition of styrenes gave the corresponding ε-hydroxylketones via the generation of benzylic radicals by the addition of alkyl radicals to styrenes and following coupling with ketyl radicals. This work demonstrates the generation of ketyl radical and alkyl radical under the photoredox cooperative NHC/Pd catalysis, and provides two and three component reactions for the synthesis of ketones from aldehydes with alkyl C(sp(3))-H functionalization. The synthetic potential of this protocol was also further illustrated by the late-stage functionalization of natural products. Nature Publishing Group UK 2023-07-08 /pmc/articles/PMC10329650/ /pubmed/37422483 http://dx.doi.org/10.1038/s41467-023-39707-8 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
Wang, Hai-Ying
Wang, Xin-Han
Zhou, Bang-An
Zhang, Chun-Lin
Ye, Song
Ketones from aldehydes via alkyl C(sp(3))−H functionalization under photoredox cooperative NHC/palladium catalysis
title Ketones from aldehydes via alkyl C(sp(3))−H functionalization under photoredox cooperative NHC/palladium catalysis
title_full Ketones from aldehydes via alkyl C(sp(3))−H functionalization under photoredox cooperative NHC/palladium catalysis
title_fullStr Ketones from aldehydes via alkyl C(sp(3))−H functionalization under photoredox cooperative NHC/palladium catalysis
title_full_unstemmed Ketones from aldehydes via alkyl C(sp(3))−H functionalization under photoredox cooperative NHC/palladium catalysis
title_short Ketones from aldehydes via alkyl C(sp(3))−H functionalization under photoredox cooperative NHC/palladium catalysis
title_sort ketones from aldehydes via alkyl c(sp(3))−h functionalization under photoredox cooperative nhc/palladium catalysis
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10329650/
https://www.ncbi.nlm.nih.gov/pubmed/37422483
http://dx.doi.org/10.1038/s41467-023-39707-8
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