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[3+2] Cycloaddition of alkyl aldehydes and alkynes enabled by photoinduced hydrogen atom transfer

[3+2] Cycloaddition is a step- and atom-economic method for the synthesis of five-membered rings. Despite the great success of 1,3-dipolar cycloadditions, the radical [3+2] annulation of alkynes remains a formidable challenge. Herein, a photoinduced decatungstate-catalyzed [3+2] cycloaddition of var...

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Autores principales: Le, Siya, Li, Ji, Feng, Jian, Zhang, Zuxiao, Bai, Yihui, Yuan, Zheliang, Zhu, Gangguo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9374768/
https://www.ncbi.nlm.nih.gov/pubmed/35961987
http://dx.doi.org/10.1038/s41467-022-32467-x
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author Le, Siya
Li, Ji
Feng, Jian
Zhang, Zuxiao
Bai, Yihui
Yuan, Zheliang
Zhu, Gangguo
author_facet Le, Siya
Li, Ji
Feng, Jian
Zhang, Zuxiao
Bai, Yihui
Yuan, Zheliang
Zhu, Gangguo
author_sort Le, Siya
collection PubMed
description [3+2] Cycloaddition is a step- and atom-economic method for the synthesis of five-membered rings. Despite the great success of 1,3-dipolar cycloadditions, the radical [3+2] annulation of alkynes remains a formidable challenge. Herein, a photoinduced decatungstate-catalyzed [3+2] cycloaddition of various internal alkynes using abundant aliphatic aldehydes as a three-carbon synthon is developed, producing elaborate cyclopentanones in 100% atom economy with excellent site-, regio-, and diastereoselectivity under mild conditions. The catalytic cycle consists of hydrogen atom abstraction from aldehydes, radical addition, 1,5-hydrogen atom transfer, anti-Baldwin 5-endo-trig cyclization, and back hydrogen abstraction. The power of this method is showcased by the late-stage elaboration of medicinally relevant molecules and total or formal synthesis of (±)-β-cuparenone, (±)-laurokamurene B, and (±)-cuparene.
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spelling pubmed-93747682022-08-14 [3+2] Cycloaddition of alkyl aldehydes and alkynes enabled by photoinduced hydrogen atom transfer Le, Siya Li, Ji Feng, Jian Zhang, Zuxiao Bai, Yihui Yuan, Zheliang Zhu, Gangguo Nat Commun Article [3+2] Cycloaddition is a step- and atom-economic method for the synthesis of five-membered rings. Despite the great success of 1,3-dipolar cycloadditions, the radical [3+2] annulation of alkynes remains a formidable challenge. Herein, a photoinduced decatungstate-catalyzed [3+2] cycloaddition of various internal alkynes using abundant aliphatic aldehydes as a three-carbon synthon is developed, producing elaborate cyclopentanones in 100% atom economy with excellent site-, regio-, and diastereoselectivity under mild conditions. The catalytic cycle consists of hydrogen atom abstraction from aldehydes, radical addition, 1,5-hydrogen atom transfer, anti-Baldwin 5-endo-trig cyclization, and back hydrogen abstraction. The power of this method is showcased by the late-stage elaboration of medicinally relevant molecules and total or formal synthesis of (±)-β-cuparenone, (±)-laurokamurene B, and (±)-cuparene. Nature Publishing Group UK 2022-08-12 /pmc/articles/PMC9374768/ /pubmed/35961987 http://dx.doi.org/10.1038/s41467-022-32467-x 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
Le, Siya
Li, Ji
Feng, Jian
Zhang, Zuxiao
Bai, Yihui
Yuan, Zheliang
Zhu, Gangguo
[3+2] Cycloaddition of alkyl aldehydes and alkynes enabled by photoinduced hydrogen atom transfer
title [3+2] Cycloaddition of alkyl aldehydes and alkynes enabled by photoinduced hydrogen atom transfer
title_full [3+2] Cycloaddition of alkyl aldehydes and alkynes enabled by photoinduced hydrogen atom transfer
title_fullStr [3+2] Cycloaddition of alkyl aldehydes and alkynes enabled by photoinduced hydrogen atom transfer
title_full_unstemmed [3+2] Cycloaddition of alkyl aldehydes and alkynes enabled by photoinduced hydrogen atom transfer
title_short [3+2] Cycloaddition of alkyl aldehydes and alkynes enabled by photoinduced hydrogen atom transfer
title_sort [3+2] cycloaddition of alkyl aldehydes and alkynes enabled by photoinduced hydrogen atom transfer
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9374768/
https://www.ncbi.nlm.nih.gov/pubmed/35961987
http://dx.doi.org/10.1038/s41467-022-32467-x
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