双噁唑啉接枝的氨基酸聚合物作为手性催化中心在不对称Henry反应中的应用  

Application of Bisoxazoline-grafted Amino Acid Polymer as Chiral Catalytic Center in Asymmetric Henry Reaction

作　　者：朱佶鹏 刘润辉[2,3,4] 宋恭华 ZHU Jipeng;LIU Runhui;SONG Gonghua(School of Pharmacy,Shanghai 200237,China;State Key Laboratory of Bioreactor Engineering,Shanghai 200237,China;Key Laboratory for Ultrafine Materials of Ministry of Education,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China;East China University of Science and Technology Shenzhen Research Institute,Shenzhen 518063,China)

机构地区：[1]华东理工大学药学院,上海200237 [2]生物反应器工程国家重点实验室,上海200237 [3]材料科学与工程学院,超细材料制备与应用教育部重点实验室,上海200237 [4]华东理工大学深圳研究院,深圳518063

出　　处：《高等学校化学学报》2023年第4期163-171,共9页Chemical Journal of Chinese Universities

基　　金：中央高校基本科研业务费专项资金和华东理工大学自由探索性基础研究项目(批准号:2021Szvup042)资助。

摘　　要：通过控制聚合单体L-谷氨酸-γ-乙酯和DL-半胱氨酸以及聚合过程中引发剂与单体的比例,制备了一系列溶解性能不同的氨基酸聚合物.利用其作为负载手性配体的载体,通过双噁唑啉配体上的双键和聚合物上巯基的加成反应,合成了一系列双噁唑啉接枝氨基酸聚合物.将合成的聚合物作为可回收的手性催化剂用于催化不对称Henry反应,反应选择性(e.e.值)在50%~90%之间,产率在67%~95%之间.该催化剂可以循环使用至少7次而不需要经过重新活化.A series of amino acid polymers with different solubility was prepared through controlling the ratio of L-Glutamic acid-1-ethyl ester to DL-cysteine and the ratio of initiator to monomer in the polymerization process.With the amino acicl polymer as carriers for chiral ligands,a series of bisoxazoline-grafted amino acid polymers was synthesized by the addition reaction between the double bond on the bisoxazoline ligand and the sulfhydryl group on the polymer.The polymers can be used as a recoverable chiral ligand to catalyze asymmetric Henry reaction.The enantiomeric excess(e.e.)value of the reaction is between 50%—90%and the yield is between 67%—95%.The catalyst can be recycled for at least 7 times without reactivation.

关 键 词：氨基酸聚合物 双噁唑啉 Henry反应 不对称催化 

分 类 号：O643[理学—物理化学]