Stereodivergent Benzylic Substitution of Racemic Secondary Benzyl Esters Enabled by Pd/Cu Dual Catalysis  

作　　者：Youbin Peng Guanlin Li Chongyu Han Yicong Luo Xiaohong Huo Wanbin Zhang 

机构地区：[1]Shanghai Key Laboratory of Molecular Engineering of Chiral Drugs,Frontiers Science Center for Transformative Molecules,School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240

出　　处：《CCS Chemistry》2024年第10期2452-2464,共13页中国化学会会刊（英文）

基　　金：supported by the National Key R&D Program of China(grant no.2023YFA1506700);the National Natural Science Foundation of China(NSFC,grant nos.21831005,21991112,and 22171183).

摘　　要：Transition-metal-catalyzed asymmetric benzylic substitution of racemic benzyl esters is an efficient and straightforward route towards the construction of benzylic stereocenters but remains a challenge,due to the difficulty encountered in the suppression ofβ–H elimination and asymmetric induction.Herein,we successfully developed a highly diastereo-and enantioselective benzylic substitution of racemic 1-(aryl)alkyl esters with aldimine esters enabled by Pd/Cu dual catalysis.An array of enantioenrichedα-benzyl substitutedα-amino acids containing vicinal stereocenters were prepared with high levels of diastereo-and enantioselectivities(up to>20:1 dr and>99%ee)and the practicability of the products was further illustrated via their diverse transformations.The dynamic kinetic asymmetric transformation process of the racemic benzyl esters was investigated experimentally and by computational studies.

关 键 词：amino acids asymmetric catalysis benzylic substitution bimetallic catalysis stereodivergent synthesis 

分 类 号：O62[理学—有机化学]