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铜催化的炔烃-烯丙基取代反应:概念与最新进展

Copper-catalyzed yne-allylic substitutions: concept and recent developments.

作者信息

Yang Shuang, Fang Xinqiang

机构信息

State Key Laboratory of Structural Chemistry, and Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Fuzhou 350100, China.

出版信息

Beilstein J Org Chem. 2024 Oct 31;20:2739-2775. doi: 10.3762/bjoc.20.232. eCollection 2024.

Abstract

The catalytic (asymmetric) allylation and propargylation have been established as powerful strategies allowing access to enantioenriched α-chiral alkenes and alkynes. In this context, combining allylic and propargylic substitutions offers new opportunities to expand the scope of transition metal-catalyzed substitution reactions. Since its discovery in 2022, copper-catalyzed yne-allylic substitution has undergone rapid development and significant progress has been made using the key copper vinyl allenylidene intermediates. This review summarizes the developments and illustrates the influences of copper salt, ligand, and substitution pattern of the substrate on the regioselectivity and stereoselectivity.

摘要

催化(不对称)烯丙基化反应和炔丙基化反应已被确立为合成对映体富集的α-手性烯烃和炔烃的有效策略。在此背景下,将烯丙基取代反应和炔丙基取代反应相结合,为拓展过渡金属催化的取代反应范围提供了新的机遇。自2022年被发现以来,铜催化的烯炔-烯丙基取代反应发展迅速,并且利用关键的铜乙烯基联烯基中间体取得了重大进展。本综述总结了该反应的发展情况,并阐述了铜盐、配体以及底物的取代模式对区域选择性和立体选择性的影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8168/11533123/63aee200729b/Beilstein_J_Org_Chem-20-2739-g002.jpg

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