(Parallel) kinetic resolution of 3,3-disubstituted indolines via organocatalyzed reactions with azodicarboxylates  

作　　者：Qianwen Jiang Dekun Zhang Mengyao Tang Hua Liu Xiaoyu Yang 

机构地区：[1]School of Physical Science and Technology,ShanghaiTech University,Shanghai 201210,China

出　　处：《Science China Chemistry》2024年第3期973-980,共8页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(22171186,22222107);ShanghaiTech University Start-up Funding;Analytical Instrumentation Center(#SPSTAIC10112914),SPST,ShanghaiTech University。

摘　　要：A novel kinetic resolution(KR) method has been developed for 3,3-disubstituted indolines, whose catalytic asymmetric synthesis remains a significant challenge in organic synthesis. The key to the success of this KR protocol lies in the utilization of chiral phosphoric acid-catalyzed triazane formation reaction with azodicarboxylates, which enables the enantioselective synthesis of various substituted indolines bearing C3-quaternary stereocenters with good to high enantioselectivities(with sfactors up to 70). Moreover, an intriguing parallel kinetic resolution(PKR) has been developed by combining triazane formation and dehydrogenation reactions using different azodicarboxylates. Experimental studies have provided insight into the mechanism of this PKR reaction, demonstrating stereoselectivity in both triazane formation and dehydrogenation steps, favoring the opposite enantiomers. The large-scale synthesis and diverse derivatizations of the products, particularly the imine groupcontaining 3H-indoles, demonstrate the value of these(P)KR methods.

关 键 词：asymmetric organocatalysis kinetic resolution 3 3-disubstituted indolines AZODICARBOXYLATE triazanes 

分 类 号：O621.251[理学—有机化学] O626[理学—化学]