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Easy access to medium-sized lactones through metal carbene migratory insertion enabled 1,4-palladium shift

Reactions that efficiently construct medium-sized lactones are significant, as they overcome the unfavorable entropic factor and transannular interactions for ring closure, and the lactones produced are common structural motifs recurring in many biologically active compounds. Herein, we describe a v...

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Autores principales: Yu, Yinghua, Chakraborty, Pushkin, Song, Jinshuai, Zhu, Lei, Li, Chunsen, Huang, Xueliang
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6978448/
https://www.ncbi.nlm.nih.gov/pubmed/31974346
http://dx.doi.org/10.1038/s41467-019-14101-5
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author Yu, Yinghua
Chakraborty, Pushkin
Song, Jinshuai
Zhu, Lei
Li, Chunsen
Huang, Xueliang
author_facet Yu, Yinghua
Chakraborty, Pushkin
Song, Jinshuai
Zhu, Lei
Li, Chunsen
Huang, Xueliang
author_sort Yu, Yinghua
collection PubMed
description Reactions that efficiently construct medium-sized lactones are significant, as they overcome the unfavorable entropic factor and transannular interactions for ring closure, and the lactones produced are common structural motifs recurring in many biologically active compounds. Herein, we describe a valuable strategy for medium-sized lactone synthesis by accomplishing site-selective C–H bond functionalization via a palladium carbene migratory insertion enabled 1,4-palladium shift. The overall process achieves the formal dimerization of two readily available benzaldehyde derivatives, providing value-added products medium-sized lactones. Our method is amenable to late-stage modification of approved drugs and other complex molecules. Mechanistic studies including deuterium-labeling experiments and DFT calculation shed light on the reaction pathways.
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spelling pubmed-69784482020-01-27 Easy access to medium-sized lactones through metal carbene migratory insertion enabled 1,4-palladium shift Yu, Yinghua Chakraborty, Pushkin Song, Jinshuai Zhu, Lei Li, Chunsen Huang, Xueliang Nat Commun Article Reactions that efficiently construct medium-sized lactones are significant, as they overcome the unfavorable entropic factor and transannular interactions for ring closure, and the lactones produced are common structural motifs recurring in many biologically active compounds. Herein, we describe a valuable strategy for medium-sized lactone synthesis by accomplishing site-selective C–H bond functionalization via a palladium carbene migratory insertion enabled 1,4-palladium shift. The overall process achieves the formal dimerization of two readily available benzaldehyde derivatives, providing value-added products medium-sized lactones. Our method is amenable to late-stage modification of approved drugs and other complex molecules. Mechanistic studies including deuterium-labeling experiments and DFT calculation shed light on the reaction pathways. Nature Publishing Group UK 2020-01-23 /pmc/articles/PMC6978448/ /pubmed/31974346 http://dx.doi.org/10.1038/s41467-019-14101-5 Text en © The Author(s) 2020 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
Yu, Yinghua
Chakraborty, Pushkin
Song, Jinshuai
Zhu, Lei
Li, Chunsen
Huang, Xueliang
Easy access to medium-sized lactones through metal carbene migratory insertion enabled 1,4-palladium shift
title Easy access to medium-sized lactones through metal carbene migratory insertion enabled 1,4-palladium shift
title_full Easy access to medium-sized lactones through metal carbene migratory insertion enabled 1,4-palladium shift
title_fullStr Easy access to medium-sized lactones through metal carbene migratory insertion enabled 1,4-palladium shift
title_full_unstemmed Easy access to medium-sized lactones through metal carbene migratory insertion enabled 1,4-palladium shift
title_short Easy access to medium-sized lactones through metal carbene migratory insertion enabled 1,4-palladium shift
title_sort easy access to medium-sized lactones through metal carbene migratory insertion enabled 1,4-palladium shift
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6978448/
https://www.ncbi.nlm.nih.gov/pubmed/31974346
http://dx.doi.org/10.1038/s41467-019-14101-5
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