Tandem asymmetric propargylic amination/carboxylative cyclization reaction to chiral 5-methylidene-2-oxazolidinones using CO_(2) as C1 synthon  

作　　者：Zheng Zhang Zhi-Hao Zhang Ying Sun Yun-Hao Tang Yi-Zhuo Yang Feng Zhou Jian Zhou 

机构地区：[1]State Key Laboratory of Petroleum Molecular&Process Engineering,Shanghai Key Laboratory of Green Chemistry and Chemical Processes,.Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development,School of Chemistry and Molecular Engineering,East China Normal University,Shanghai 200062,China [2]State Key Laboratory of Organometallic Chemistry,Shanghai Instiute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China

出　　处：《Science China Chemistry》2025年第4期1402-1411,共10页中国科学(化学英文版)

基　　金：supported by the National Natural Science Foundation of China(21871090,21725203);the National Key Research and Development Program of China(2020YFA0710200);the Shanghai Science and Technology Innovation Action Plan(20JC1416900);the Innovation Program of Shanghai Municipal Education Commission(2023ZKZD37);the Fundamental Research Funds for the Central Universities.

摘　　要：We report a tandem asymmetric Cu-catalyzed propargylic amination(ACPA)/Ag-catalyzed carboxylative cyclization(SCC)with CO_(2) to 5-methylidene-2-oxazolidinones;even with tetrasubstituted stereocenters.By varying pyridine bisoxazoline(PYBOX)ligands;a general and highly enantioselective ACPA of unprecedentedly broad scope of secondary propargylic acetates and primary amines is achieved.Bothα-aryl andα-aliphatic propargylic acetates could react with either aromatic or aliphatic primary amines to give the corresponding N-aryl or N-aliphatic ethynylamines withα-aliphatic orα-aryl groups in over 90%ee for use in the next step.The key to developing this one-pot sequence is to use a chelator triethylenetetramine(TETA)to mask the copper ion;to avoid its negative effect on Ag-catalyzed cyclization;whilst releasing PYBOX to activate the silver catalyst.With the methylidene moiety;these oxazolidinones can be readily elaborated.The value of the sequence is further shown by the catalytic enantioselective total synthesis of(–)-cytoxazone and the potent ezetimibe analogue.

关 键 词：CO_(2) 2-oxazolidinone tandem sequence propargylic amination carboxylative cyclization 

分 类 号：O626[理学—有机化学]