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Cu(ii)-mediated direct intramolecular cyclopropanation of distal olefinic acetate: access to cyclopropane-fused γ-lactones
Cyclopropane-fused ring scaffolds represent one of the most appealing structural motifs in organic chemistry due to their wide presence in bioactive molecules and versatility in organic synthesis. These skeletons are typically prepared from olefinic diazo compounds via transition-metal catalysed int...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10284120/ https://www.ncbi.nlm.nih.gov/pubmed/37350833 http://dx.doi.org/10.1039/d3sc01752d |
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author | Wang, Yulong Shen, Shenyu He, Chonglong Zhou, Youkang Zhang, Keyuan Rao, Bin Han, Tian Su, Yaqiong Duan, Xin-Hua Liu, Le |
author_facet | Wang, Yulong Shen, Shenyu He, Chonglong Zhou, Youkang Zhang, Keyuan Rao, Bin Han, Tian Su, Yaqiong Duan, Xin-Hua Liu, Le |
author_sort | Wang, Yulong |
collection | PubMed |
description | Cyclopropane-fused ring scaffolds represent one of the most appealing structural motifs in organic chemistry due to their wide presence in bioactive molecules and versatility in organic synthesis. These skeletons are typically prepared from olefinic diazo compounds via transition-metal catalysed intramolecular carbenoid insertion, which suffers from prefunctionalization of starting materials and limited substrate scope. Herein, we disclose a practical copper-mediated direct intramolecular cyclopropanation of distal olefinic acetate to synthesize cyclopropane-fused γ-lactones and lactams. This cascade reaction is postulated to proceed through a hydrogen atom transfer event induced radical cyclization and copper-mediated cyclopropanation sequence. The protocol features high atom- and step-economy, excellent diastereoselectivity, broad tolerance of functional groups, and operational simplicity. |
format | Online Article Text |
id | pubmed-10284120 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-102841202023-06-22 Cu(ii)-mediated direct intramolecular cyclopropanation of distal olefinic acetate: access to cyclopropane-fused γ-lactones Wang, Yulong Shen, Shenyu He, Chonglong Zhou, Youkang Zhang, Keyuan Rao, Bin Han, Tian Su, Yaqiong Duan, Xin-Hua Liu, Le Chem Sci Chemistry Cyclopropane-fused ring scaffolds represent one of the most appealing structural motifs in organic chemistry due to their wide presence in bioactive molecules and versatility in organic synthesis. These skeletons are typically prepared from olefinic diazo compounds via transition-metal catalysed intramolecular carbenoid insertion, which suffers from prefunctionalization of starting materials and limited substrate scope. Herein, we disclose a practical copper-mediated direct intramolecular cyclopropanation of distal olefinic acetate to synthesize cyclopropane-fused γ-lactones and lactams. This cascade reaction is postulated to proceed through a hydrogen atom transfer event induced radical cyclization and copper-mediated cyclopropanation sequence. The protocol features high atom- and step-economy, excellent diastereoselectivity, broad tolerance of functional groups, and operational simplicity. The Royal Society of Chemistry 2023-05-25 /pmc/articles/PMC10284120/ /pubmed/37350833 http://dx.doi.org/10.1039/d3sc01752d Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Wang, Yulong Shen, Shenyu He, Chonglong Zhou, Youkang Zhang, Keyuan Rao, Bin Han, Tian Su, Yaqiong Duan, Xin-Hua Liu, Le Cu(ii)-mediated direct intramolecular cyclopropanation of distal olefinic acetate: access to cyclopropane-fused γ-lactones |
title | Cu(ii)-mediated direct intramolecular cyclopropanation of distal olefinic acetate: access to cyclopropane-fused γ-lactones |
title_full | Cu(ii)-mediated direct intramolecular cyclopropanation of distal olefinic acetate: access to cyclopropane-fused γ-lactones |
title_fullStr | Cu(ii)-mediated direct intramolecular cyclopropanation of distal olefinic acetate: access to cyclopropane-fused γ-lactones |
title_full_unstemmed | Cu(ii)-mediated direct intramolecular cyclopropanation of distal olefinic acetate: access to cyclopropane-fused γ-lactones |
title_short | Cu(ii)-mediated direct intramolecular cyclopropanation of distal olefinic acetate: access to cyclopropane-fused γ-lactones |
title_sort | cu(ii)-mediated direct intramolecular cyclopropanation of distal olefinic acetate: access to cyclopropane-fused γ-lactones |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10284120/ https://www.ncbi.nlm.nih.gov/pubmed/37350833 http://dx.doi.org/10.1039/d3sc01752d |
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