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作 者:陈运荣 刘炜 杨晓瑜 Chen Yunrong;Liu Wei;Yang Xiaoyu(School of Physical Science and Technology,ShanghaiTech University,Shanghai 201210)
机构地区:[1]上海科技大学物质科学与技术学院,上海201210
出 处:《有机化学》2022年第3期679-697,共19页Chinese Journal of Organic Chemistry
基 金:国家自然科学基金(Nos.21901162,22171186);上海科技大学启动基金资助项目.
摘 要:手性叔醇结构广泛存在于生物活性物质、天然产物和药物分子中,实现其高效不对称催化合成具有重要意义.消旋醇的动力学拆分是一种合成高光学纯度手性醇的重要方法,然而由于叔醇α-碳上带三个不同的非氢取代基团,手性识别难度较大,因而发展高效且具有广泛底物适用性的叔醇动力学拆分方法具有较大的挑战.尽管如此,近年来非酶催化的叔醇的动力学拆分领域取得了快速的发展,一些新颖的不对称催化反应、催化体系被成功应用于叔醇的动力学拆分反应中.对叔醇动力学拆分反应进行了系统总结,分类介绍了这些反应的底物适用性、特点、机理以及局限等,并对该领域的未来发展进行展望.Chiral tertiary alcohol is widely present in a series of bioactive compounds,natural products and pharmaceuticals.Consequently,the development of efficient asymmetric catalytic methods for their syntheses is highly important.Kinetic resolution(KR)is an important strategy to access enantioenriched alcohols from racemic alcohols.However,due to the requirement to distinguish three none-hydrogen substituents at theα-position of tertiary alcohols,it is challenging to develop highly efficient kinetic resolution protocols for tertiary alcohols with broad substrate scope.Nevertheless,significant progress has been made in the field of nonenzymatic kinetic resolution of tertiary alcohols in recent years,and a number of novel asymmetric reactions and catalytic systems have been successfully applied in the KR of tertiary alcohols.The tremendous advances in the kinetic resolution of tertiary alcohols are comprehensively reviewed,the substrate scope,characteristics,mechanisms and limitations of these methods are summarized,and our perspective on this research field is also provided.
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