Synthesis of Planar-Chiral[2.2]Paracyclophane-Based Oxazole-Pyrimidine Ligands and Application in Nickel-Catalyzed 1,2-Reduction ofα,β-Unsaturated Ketones  

作　　者：Juan Wang Qing-Xian Xie Xiang Li Chang-Bin Yu Yong-Gui Zhou 

机构地区：[1]School of Chemistry,Dalian University of Technology,2 Linggong Road,Dalian,Liaoning 116024,China [2]State Key Laboratory of Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian,Liaoning 116023,China

出　　处：《Chinese Journal of Chemistry》2024年第7期705-710,共6页中国化学（英文版）

基　　金：Financial support from National Natural Science Foundation of China (22171260);K.C.Wong Education Foundation of CAS (GJTD-2020-08)is acknowledged.

摘　　要：The planar-chiral ligands have been widely applied as a class of unique and significant ligands in asymmetric catalysis.Among them,chiral[2.2]paracycyclophane has emerged as a privileged type of planar-chiral framework and has been utilized as an important toolbox due to their structural stability.Herein,we design and synthesize[2.2]paracyclophane-derived oxazole-pyrimidine ligands(abberviated as PYMCOX).These N,N-ligands with stable properties,rigid structure and large steric hindrance performed successfully in nickel-catalyzed asymmetric 1,2-reduction ofα,β-unsaturated ketones,affording the chiral allylic alcohols with up to 99%yield and 99%ee.Meanwhile,this reduction reaction could be conducted on gram-scale without loss of activity and enantioselectivity,and the chiral ligand could be conveniently recovered with high yield.

关 键 词：Oxazole-pyrimidine ligands Planar chirality Nickel HYDROBORATION Asymmetric synthesis 

分 类 号：O62[理学—有机化学]