手性双氮氧/金属配合物催化叶立德不对称反应的研究进展  

Progress in N,N′-dioxide/metal complex-catalyzed asymmetric reactions of ylides

作　　者：林丽丽 周宇乔 曹伟地 董顺喜 刘小华 冯小明[1] Lili Lin;Yuqiao Zhou;Weidi Cao;Shunxi Dong;Xiaohua Liu;Xiaoming Feng(Key Laboratory of Green Chemistry&Technology,Ministry of Education,College of Chemistry,Sichuan University,Chengdu 610064,China)

机构地区：[1]四川大学化学学院绿色化学与技术教育部重点实验室,成都610064

出　　处：《中国科学：化学》2023年第3期246-258,共13页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:22188101,21890723)资助项目。

摘　　要：叶立德作为内盐分子,活性高、种类和反应类型多样,极具吸引力,是合成含杂原子化合物的重要工具.另一方面,冯氏手性双氮氧配体作为优势配体,结构高度可调,与主族、过渡金属和稀土金属等形成配合物已催化众多不对称反应.本文介绍了手性双氮氧/金属配合物作为路易斯酸催化剂、与过渡金属或光敏试剂组合催化等方式,实现硫叶立德、氮叶立德和碘叶立德的不对称转化,涉及不对称加成、环化、重排、串联等,并重点关注关键的反应过程和手性诱导机理.最后,展望了手性双氮氧/金属配合物催化叶立德不对称反应的挑战和前景.Ylides,as inner salt molecules,possess the properties of high activity and diverse reactivity.They are attractive for their convenient synthesis of compounds containing heteroatom.On the other hand,privileged Feng C2 symmetric N,N′-dioxide ligands can coordinate with plenty of main group metals,transition metals,and rare earth metals,offering the opportunity to efficiently catalyze more than 70 types of asymmetric reactions.In this article,the N,N′-dioxide/metal complexes-promoted asymmetric reactions of sulfur ylides,nitrium ylides and iodonium ylides were reviewed,including asymmetric addition,cycloaddition,rearrangement and domino reactions,through Lewis acid catalysis,bimetallic relay catalysis,and photocatalysis.The possible reaction mechanism including transition state was emphasized.Last,the challenges and prospects of the N,N′-dioxide/metal complex-promoted asymmetric reactions of ylides were discussed.

关 键 词：不对称催化 叶立德 手性双氮氧/金属配合物 环加成 重排 串联反应 

分 类 号：O641.4[理学—物理化学] O621.251[理学—化学]