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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...

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Autores principales: Wang, Yulong, Shen, Shenyu, He, Chonglong, Zhou, Youkang, Zhang, Keyuan, Rao, Bin, Han, Tian, Su, Yaqiong, Duan, Xin-Hua, Liu, Le
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2023
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.
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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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