Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents

While aldehydes represent a classic class of electrophilic synthons, the corresponding acyl radicals are inherently nucleophilic, which exhibits umpolung reactivity. Generation of acyl radicals typically requires noble metal catalysts or excess oxidants to be added. Herein, we report a convenient an...

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Autores principales: Yan, Jianming, Tang, Haidi, Kuek, Eugene Jun Rong, Shi, Xiangcheng, Liu, Chenguang, Zhang, Muliang, Piper, Jared L., Duan, Shengquan, Wu, Jie
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2021
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Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8664905/
https://www.ncbi.nlm.nih.gov/pubmed/34893628
http://dx.doi.org/10.1038/s41467-021-27550-8
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author Yan, Jianming
Tang, Haidi
Kuek, Eugene Jun Rong
Shi, Xiangcheng
Liu, Chenguang
Zhang, Muliang
Piper, Jared L.
Duan, Shengquan
Wu, Jie
author_facet Yan, Jianming
Tang, Haidi
Kuek, Eugene Jun Rong
Shi, Xiangcheng
Liu, Chenguang
Zhang, Muliang
Piper, Jared L.
Duan, Shengquan
Wu, Jie
author_sort Yan, Jianming
collection PubMed
description While aldehydes represent a classic class of electrophilic synthons, the corresponding acyl radicals are inherently nucleophilic, which exhibits umpolung reactivity. Generation of acyl radicals typically requires noble metal catalysts or excess oxidants to be added. Herein, we report a convenient and green approach to access acyl radicals, capitalizing on neutral eosin Y-enabled hydrogen atom transfer (HAT) photocatalysis with aldehydes. The generated acyl radicals underwent SOMOphilic substitutions with various functionalized sulfones (X–SO(2)R’) to deliver value-added acyl products. The merger of eosin Y photocatalysis and sulfone-based SOMOphiles provides a versatile platform for a wide array of aldehydic C–H functionalizations, including fluoromethylthiolation, arylthiolation, alkynylation, alkenylation and azidation. The present protocol features green characteristics, such as being free of metals, harmful oxidants and additives; step-economic; redox-neutral; and amenable to scale-up assisted by continuous-flow technology.
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spelling pubmed-86649052021-12-27 Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents Yan, Jianming Tang, Haidi Kuek, Eugene Jun Rong Shi, Xiangcheng Liu, Chenguang Zhang, Muliang Piper, Jared L. Duan, Shengquan Wu, Jie Nat Commun Article While aldehydes represent a classic class of electrophilic synthons, the corresponding acyl radicals are inherently nucleophilic, which exhibits umpolung reactivity. Generation of acyl radicals typically requires noble metal catalysts or excess oxidants to be added. Herein, we report a convenient and green approach to access acyl radicals, capitalizing on neutral eosin Y-enabled hydrogen atom transfer (HAT) photocatalysis with aldehydes. The generated acyl radicals underwent SOMOphilic substitutions with various functionalized sulfones (X–SO(2)R’) to deliver value-added acyl products. The merger of eosin Y photocatalysis and sulfone-based SOMOphiles provides a versatile platform for a wide array of aldehydic C–H functionalizations, including fluoromethylthiolation, arylthiolation, alkynylation, alkenylation and azidation. The present protocol features green characteristics, such as being free of metals, harmful oxidants and additives; step-economic; redox-neutral; and amenable to scale-up assisted by continuous-flow technology. Nature Publishing Group UK 2021-12-10 /pmc/articles/PMC8664905/ /pubmed/34893628 http://dx.doi.org/10.1038/s41467-021-27550-8 Text en © The Author(s) 2021 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
Yan, Jianming
Tang, Haidi
Kuek, Eugene Jun Rong
Shi, Xiangcheng
Liu, Chenguang
Zhang, Muliang
Piper, Jared L.
Duan, Shengquan
Wu, Jie
Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents
title Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents
title_full Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents
title_fullStr Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents
title_full_unstemmed Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents
title_short Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents
title_sort divergent functionalization of aldehydes photocatalyzed by neutral eosin y with sulfone reagents
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8664905/
https://www.ncbi.nlm.nih.gov/pubmed/34893628
http://dx.doi.org/10.1038/s41467-021-27550-8
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