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使用1,6-烯炔与1,1-二取代烯烃的立体选择性过渡金属催化[(2+2)+1]和[(2+2)+2]碳环化反应：季碳中心的构建

Stereoselective transition metal-catalyzed [(2+2)+1] and [(2+2)+2] carbocyclization reactions using 1,6-enynes with 1,1-disubstituted olefins: construction of quaternary centers.

作者信息

Ylagan Ridge Michael P, Zhu Yu, Evans P Andrew

机构信息

Department of Chemistry, Queen's University 90 Bader Lane Kingston Ontario K7L 3N6 Canada

Xiangya School of Pharmaceutical Sciences, Central South University Changsha 410013 Hunan China.

出版信息

Chem Sci. 2024 Sep 12;16(4):1490-1505. doi: 10.1039/d4sc02645d. eCollection 2025 Jan 22.

DOI:10.1039/d4sc02645d
PMID:39713758
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11656196/
Abstract

Transition metal-catalyzed carbocyclization reactions provide a powerful method for the stereoselective assembly of complex, highly substituted (poly)cyclic scaffolds. Although 1,6-enynes are common substrates for these transformations, using polysubstituted alkene derivatives to construct functionalized cyclic products remains challenging due to their significantly lower reactivity. This highlights key developments in stereoselective semi-intramolecular metal-catalyzed [(2+2)+1] and [(2+2)+2] carbocyclizations of 1,6-enynes containing 1,1-disubstituted alkenes, which produce cycloadducts with quaternary stereogenic centers. The insights gleaned from these examples provide a blueprint for developing more general carbocyclization strategies with challenging polysubstituted olefins.

摘要

过渡金属催化的碳环化反应为复杂的、高度取代的（多）环骨架的立体选择性组装提供了一种强大的方法。尽管1,6-烯炔是这些转化反应的常见底物，但使用多取代烯烃衍生物构建功能化环状产物仍然具有挑战性，因为它们的反应活性显著较低。本文重点介绍了含1,1-二取代烯烃的1,6-烯炔的立体选择性半分子内金属催化[(2+2)+1]和[(2+2)+2]碳环化反应的关键进展，这些反应生成具有季碳立体中心的环加成产物。从这些例子中获得的见解为开发更通用的、针对具有挑战性的多取代烯烃的碳环化策略提供了蓝图。

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