摘要/Abstract
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受酶变构催化的启发,人工刺激响应不对称催化体系的研究近年来愈来愈引起人们的兴趣.通过将刺激响应性官能团引入手性催化剂的设计,利用光驱动、配位驱动、pH驱动以及氧化还原驱动等方式,动态调控催化反应的活性和对映选择性,成功实现了多类可切换不对称催化反应.主要介绍了近20年来人工刺激响应性不对称催化体系的发展与研究现状.通过选择代表性的研究成果,从刺激响应模块与催化位点的有机结合和动态调控出发,阐述其作为手性开关催化剂或者立体发散性合成催化剂的设计原理、作用机制以及他们在不对称催化反应中的应用.同时对这一新兴领域的优势和局限进行总结,并对其发展前景进行展望.
关键词: 不对称催化, 刺激响应, 手性开关催化剂, 变构催化, 对映选择性发散催化
Inspired by enzyme allosteric catalysis, the study on artificial stimuli-responsive asymmetric catalytic systems has attracted more and more attentions in recent years. In order to precisely control the catalytic activity and stereoselectivity, stimuli-responsive functionalities have been introduced into the catalyst design. A variety of asymmetric reactions featuring on/off-switchable catalysis and/or stereodivergent catalysis have been successfully achieved by using light-, coordination-, pH-and redox-driven chiral switchable catalysts. By selecting representative examples, the catalyst design principles, allosteric mechanism and their applications in switchable asymmetric reactions sre mainly introduced. At the same time, advantages and limitations of this emerging field are summarized, and perspectives for its future development are given.
Key words: asymmetric catalysis, stimuli-responsiveness, chiral switchable catalyst, allosteric catalysis, enantiodivergent catalysis
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