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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...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2020
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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. |
format | Online Article Text |
id | pubmed-6978448 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
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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