过渡金属催化的不对称共轭烯丙基化反应研究进展

doi:10.6023/A26090313

综述

过渡金属催化的不对称共轭烯丙基化反应研究进展

李晖^a,*, 殷亮^b,*

^a运城学院化学与材料系运城 044000;
^b中国科学院上海有机化学研究所先进氟氮材料全国重点实验室上海 200032

投稿日期:2026-09-08
通讯作者: ^*E-mail: lihuiwf@ycu.edu.cn; liangyin@sioc.ac.cn; Tel.: 021-54925168
作者简介:李晖, 运城学院化学与材料系副教授. 本科毕业于南开大学; 硕士毕业于天津大学(导师: 姜申德教授). 主要从事铜催化的不对称插烯反应研究和药物中间体合成工艺研究等.殷亮, 中国科学院上海有机化学研究所研究员、课题组长. 本科和硕士毕业于南开大学; 博士毕业于东京大学(导师: Masakatsu Shibasaki教授和Motomu Kanai教授). 主要从事一价铜不对称催化的C-C键和C-X键成键反应研究.
基金资助:
中国科学院战略性先导科技专项(XDB1640000)和山西省基础研究计划(202303021211189).

Research Progress on Transition-Metal-Catalyzed Asymmetric Conjugate Allylations

Li, Hui^a,*, Yin, Liang^b,*

^aDepartment of Chemistry and Materials, Yuncheng University, Yuncheng 044000;
^bState Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China

Received:2026-09-08
Supported by:
Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB1640000) and Natural Science Foundation of Shanxi Province (No. 202303021211189).

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摘要/Abstract

手性β-烯丙基羰基化合物是一类重要的手性结构单元, 这类骨架广泛存在于多种具有生物活性的天然产物分子中. 因此, 手性β-烯丙基羰基结构片段的合成受到合成化学家们的重视. 在过渡金属催化下, α,β-不饱和羰基化合物与原位生成的烯丙基金属物种的不对称共轭加成反应是合成手性β-烯丙基羰基化合物最直接高效的方法之一. 此综述根据不同的亲电底物类型, 从α,β-α’,β’-不饱和酮的不对称共轭烯丙基化、2-芳亚基(烷亚基)-1,3-二羰基化合物的不对称共轭烯丙基化和不含活化基团的简单α,β-不饱和酯的不对称共轭烯丙基化三个方面对不对称共轭烯丙基化反应的研究进展进行了总结. 同时, 对一些代表性反应的机理和产物的合成应用做了介绍, 并对该领域的研究前景做了展望.

关键词: 过渡金属催化, 不对称催化, α,β-不饱和羰基化合物, 不对称共轭烯丙基化反应, 烯丙基金属物种

Chiral β-allyl carbonyl compounds are important chiral building blocks, which are ubiquitously found in biologically active natural products. Therefore, the development of efficient strategies for the synthesis of chiral β-allyl carbonyls has attracted extensive attention from synthetic chemists and has emerged as a prominent research focus in recent years. Transition-metal-catalyzed asymmetric conjugate allylation of α,β-unsaturated carbonyl compounds represents one of the most straightforward and efficient methodologies for the synthesis of enantiomerically enriched β-allyl carbonyl compounds. The in situ generated allyl metal species serve as active nucleophiles in this reaction. According to the types of electrophilic substrates, recent advances in this field are classified into three categories: asymmetric conjugate allylation of α,β-α’,β’-diunsaturated ketones, 2-arylidene(alkylidene)-1,3-dicarbonyl compounds, and simple α,β-unsaturated carbonyl compounds. The mechanisms and potential applications of some representative methodologies are briefly discussed. Finally, the future perspectives of this field are presented.

Key words: transition metal catalysis, asymmetric catalysis, α,β-unsaturated carbonyl compounds, asymmetric conjugate allylation, allyl metal species

引用此文

李晖, 殷亮. 过渡金属催化的不对称共轭烯丙基化反应研究进展[J]. 化学学报, doi: 10.6023/A26090313.

Li, Hui, Yin, Liang. Research Progress on Transition-Metal-Catalyzed Asymmetric Conjugate Allylations[J]. Acta Chimica Sinica, doi: 10.6023/A26090313.

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