含N-O多官能手性配体/Cu/Sm催化醛的不对称Henry反应研究  

Asymmetric Henry Reaction of Aldehydes Catalyzed by a Heterobimetallic Cu-Sm Complex

作　　者：何飞龙 刘亚军 周辉[2] 梁国娟[2] He Feilong;Liu Yajun;Zhou Hui;Liang Guojuan(Pharmacy Department,Chengdu Fifth People’s Hospital,Chengdu,Sichuan 611130,China;School of Pharmaceutical Science,Chongqing Medical University,Chongqing 400016,China)

机构地区：[1]成都市第五人民医院药剂科,四川成都611130 [2]重庆医科大学药学院,重庆400016

出　　处：《化学世界》2020年第7期476-486,共11页Chemical World

基　　金：重庆市自然科学基金(No.cstc2016jcyjA0250)资助项目。

摘　　要：合成了几个含N-O多官能手性配体与铜、钐原位生成杂双金属络合物用于催化醛的不对称Henry反应,得到一系列手性β-硝基醇化合物,产物结构经1H NMR,13C NMR和高分辨率质谱(HR-MS)表证。通过控制实验和非线性效应的研究,推测催化体系中单聚双金属Cu/Sm/L2络合物为催化反应的活性中心,是不对称Henry反应获得高对映选择性(最高达82%ee)和高反应收率(最高为94%)的重要影响因素。Several N-O-containing multifunctional chiral ligands were synthesized and used to in situ construct a new heterobimetallic Cu-Sm complex with copper and samarium,for catalyzing the asymmetric Henry reaction with good enantioselectivities(up to 82%ee)and good yields(up to 94%).The structure of products was confirmed by 1H NMR,13C NMR and high resolution mass spectrometry(HR-MS).The results of control experiments and nonlinear effect indicated that the monomeric bimetallic Cu/Sm/L2 complex might be the active species and it might play a key role for high stereoselectivities and high yields.

关 键 词：不对称催化 杂双金属催化剂 铜 钐 Henry反应 

分 类 号：O621[理学—有机化学]