Pd-catalyzed asymmetric carbonyl alkynylation:Synthesis of axial chiral ynones  

作　　者：Long Jin Jian Han Dongmei Fang Min Wang Jian Liao 

机构地区：[1]Natural Products Research Center,Chengdu Institute of Biology,Chinese Academy of Sciences,Chengdu 610041,China [2]College of Chemical Engineering,Sichuan University,Chengdu 610065,China [3]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Chinese Chemical Letters》2024年第6期293-297,共5页中国化学快报（英文版）

基　　金：supported financially by National Nature Science Foundation of China(No.22171258);the Youth Innovation Promotion Association CAS(No.2022375);the Biological Resources Programme,Chinese Academy of Sciences(No.KFJ-BRP-008);the Sichuan Science and Technology Program(No.2022ZYD0038)。

摘　　要：Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis,thus great efforts have been devoted to their preparation.While,introducing prochiral substrates to construct ynones bearing a chiral framework is unrealized to date.Herein,we reported the first example of Pd/SOP-catalyzed asymmetric carbonylative alkynylation via a non-classical carbonylative Sonogashiratype approach(acyl-Pd(Ⅱ)species generated from nucleophiles).By using cyclic diaryliodonium salts as prochiral substrates,various axial chiral ynones with good functional group tolerance(39 examples),satisfied yields(71%-96%)and excellent enantioselectivities(generally 94%-99%ee)were produced.Synthesis of bioactive compounds,scale-up experiment and useful transformations were also conducted to demonstrate the utility of this process.

关 键 词：PD-CATALYZED Axial chiral ynones Cyclic diaryliodonium High-valent palladium catalyzed Asymmetric carbonyl alkynylation 

分 类 号：TQ224.2[化学工程—有机化工]