Catalytically generated noncovalent ammonium dienolate:a versatile platform for the development of organocatalytic asymmetric cascade reactions  

作　　者：Jun-Bing Lin Dong-Sheng Ji Peng-Fei Xu 

机构地区：[1]State Key Laboratory of Applied Organic Chemistry,College of Chemistry and Chemical Engineering,Lanzhou University,Lanzhou 730000,China [2]Shaanxi Key Laboratory of Chemical Reaction Engineering,College of Chemistry and Chemical Engineering,Yan’an University,Yan’an 716000,China

出　　处：《Science China Chemistry》2024年第8期2524-2546,共23页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China (21871116, U22A20390);the Fundamental Research Funds for the Central Universities (lzujbky-2023-stlt01);the“111” program from the MOE of China。

摘　　要：Organocatalytic cascade reactions represent a powerful strategy for the rapid construction of complex chiral molecules with multiple stereocenters from simple substrates under mild conditions. The intriguing structural feature and diverse reactivity of catalytically generated dienolate species render them competent and versatile intermediates for the development of practical and valuable cascade reactions. Over the past years, a plethora of innovative and pioneering noncovalent ammonium dienolatemediated cascade reactions have been designed and implemented under the catalysis of chiral organocatalysts, making dienolate activation a general, robust, and complementary method for the functionalization of unsaturated carbonyl compounds and related substances. This review illustrates the recent advances in organocatalytic noncovalent ammonium dienolate-mediated cascade reactions(mainly from 2010 to 2023), including the cascade transformations of ammonium dienolates directly generated from unsaturated ketone/aldehyde, ester/lactone/azlactone, amide/lactam/pyrazolone/oxindole, and alkylidene nitrile compounds. The contents are arranged based on the reaction types of the ammonium dienolates, with an emphasis on cascade 2,5-, 3,5-, and 4,5-difunctionalizations of these intermediates. Furthermore, other cascade reactions involving the 1,3-, 2,3-, and even more complex 3,4,5-reactivities of ammonium dienolates were also discussed. The reaction pathway, reaction stereoinduction, and synthetic applications of the ammonium dienolate-mediated cascade reactions were highlighted throughout the article. As a stimulating and ever-growing research area, the organocatalytic noncovalent ammonium dienolate-mediated cascade reactions are expected to continue demonstrating their magic power for constructing chiral targets in the future and further expanding the boundaries of asymmetric catalysis.

关 键 词：ORGANOCATALYSIS asymmetric catalysis ammonium dienolate cascade reaction difunctionalization 

分 类 号：O621.251[理学—有机化学]