摘要
过去十年中,硫脲-有机膦通过有机膦或双试剂催化模式已被广泛用于各种不对称反应的催化体系中.本文通过氨基酸衍生的膦-硫脲配体和金属铜盐结合发展了一种协同催化策略,并且用于不对称(3+2)环加成和动力学拆分中,以高产率(83%~96%)和良好的对映选择性(49%~93%ee)高效地合成了一系列吡唑啉酮化合物.进一步进行了机理研究,并制备了具有催化活性Cu(Ⅰ)物种的晶体,为铜离子与膦-硫脲的相互作用进行了有价值的探索.
Over the last decade,phosphine-(thio)ureas have been extensively used as bifunctional catalysts in a variety of asymmetric reactions via organophosphine or dual-reagent catalysis.By combination of phosphine-thioureas and copper salts in this article,we developed asymmetric cooperative catalysis which served as an efficient strategy for asymmetric(3+2)cycloaddition and kinetic resolutions.The reactions gave the pyrazolone scaffolds with high yields and good enantioselectivities.Broad substrate scope was demonstrated.Notably,the crystal structure of the active Cu(Ⅰ)-species was obtained,providing valuable insight into the interaction of copper and phosphine-thioureas.
作者
余龙辉
潘仁明
刘俊
郑昌武
赵刚
Longhui Yu;Renming Pan;Jun Liu;Changwu Zheng;Gang Zhao(Key Laboratory of Synthetic Chemistry of Natural Substances,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China;Innovation Research Institute of Traditional Chinese Medicine,School of Pharmacy,Shanghai University of Traditional Chinese Medicine,Shanghai 201203,China)
出处
《中国科学：化学》
CAS
CSCD
北大核心
2023年第3期572-578,共7页
SCIENTIA SINICA Chimica
基金
国家自然科学基金(编号:21871282)资助项目。
关键词
协同催化
硫脲-有机膦
(3+2)环加成
动力学拆分
铜催化
cooperative catalysis
phosphine-thiourea
(3+2)cycloaddition
kinetic resolution
copper catalysis
