Asymmetric Autotandem Palladium Catalysis forα,β-Unsaturated Lactones:Merging Olefin and Ester Hydrogenation  

作　　者：Lei Sun Han Wang Die Bai Chang-Bin Yu Bo Wu Rong-Zhen Liao Yong-Gui Zhou 

机构地区：[1]State Key Laboratory of Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,Liaoning [2]School of Chemistry and Chemical Engineering,Huazhong University of Science and Technology,Wuhan 430074,Hubei

出　　处：《CCS Chemistry》2024年第8期1987-1999,共13页中国化学会会刊（英文）

基　　金：the National Natural Science Foundation of China(grant no.22171260);the K.C.Wong Education Foundation(grant no.GJTD-2020-08);the Bureau of Science and Technology(grant no.XLYC2002080)of Liaoning Province for financial support.

摘　　要：Autotandem catalysis(ATC)is fascinating since a single catalyst can promote tandem reactions involving two or more mechanisms in a single reactor and is a highly desirable approach to realize multifarious transformations in organic synthetic chemistry.Herein,a palladium-catalyzed asymmetric autotandem hydrogenation ofα,β-unsaturated lactones is disclosed,providing chiral saturated alcohols.In this reaction,the C=C bond inα,β-unsaturated lactones was first hydrogenated to give the dihydrocoumarins with high enantioselectivity,followed by hydrogenation of the ester group with the same catalytic system.Notably,after decreasing the reaction temperature,hydrogenation of the single C=C bond proceeded smoothly,delivering the dihydrocoumarin products with high yield and enantioselectivity.Control experiments and density functional theory calculations were carried out to elucidate the cause of this unusual asymmetric autotandem hydrogenation.Notably,the homogeneous palladium catalyst was successfully applied in the hydrogenation of esters under neutral conditions.

关 键 词：autotandem catalysis asymmetric hydrogenation chiral dihydrocoumarins hydrogenation of esters α β-unsaturated esters 

分 类 号：O62[理学—有机化学]