Chiral Betaine-Mediated Asymmetric Peroxidation-Kinetic Resolution Cascade for the Synthesis of Optically Pure Peroxides  

作　　者：Xiangyuan Liu Kang Du Jisheng Luo Li Deng 

机构地区：[1]Department of Chemistry,Zhejiang University,Hangzhou 310027 [2]Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province,Department of Chemistry,School of Science and Research Center for Industries of the Future,Westlake University,Hangzhou 310030

出　　处：《CCS Chemistry》2023年第7期1509-1516,共8页中国化学会会刊（英文）

基　　金：We gratefully acknowledge funding from the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(grant no.2020R01004);the National Natural Science Foundation of China(grant no.U22A20389).

摘　　要：An array of natural products bearing chiral peroxide motifs display antitumor,anticancer,and antiparasitic activities.However,there are very few catalytic asymmetric syntheses of chiral peroxides.Moreover,effective catalysts for asymmetric catalytic peroxidations are limited to chiral amines.To further expand synthetic access to chiral peroxides,the development of new catalysts realizing catalytic asymmetric peroxidation is highly desirable yet challenging.We report here a catalytic asymmetric peroxidation of anα,β-unsaturated triflone-kinetic resolution cascade reaction,which furnishes chiral peroxides in greater than 99.9%ee.The realization of this cascade reaction resulted from the development of two betaines as novel catalysts for chiral peroxide synthesis;one betaine promoted enantioselective peroxidation ofα,β-unsaturated triflones via conjugate addition affording peroxides in 80-92%ee,while the other betaine catalyzed kinetic resolution of the newly generated chiral peroxides to further increase the ee to greater than 99.9%.

关 键 词：chiral peroxide PEROXIDATION kinetic resolution BETAINE optically pure triflone 

分 类 号：O62[理学—有机化学]