Development of Novel Phosphino-Oxazoline Ligands and Their Application in Asymmetric Alkynlylation of Benzylic Halides  

作　　者：Rui Guo Jiale Sang Haijing Xiao Junxia Li Guozhu Zhang 

机构地区：[1]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Center for Excellence in Molecular Synthesis,University of Chinese Academy of Sciences,Chinese Academy of Sciences,345 Lingling Road,Shanghai 200032,China [2]CCNU-uOttawa Joint Research Centre,Key Laboratory of Pesticides&Chemical Biology Ministry of Education,International Joint Research Center for Intelligent Biosensing Technology and Health,College of Chemistry,Central China Normal University(CCNU),152 Luoyu Road,Wuhan,Hubei 430079,China

出　　处：《Chinese Journal of Chemistry》2022年第11期1337-1345,共9页中国化学（英文版）

基　　金：We are grateful to the National Natural Science Foundation of China(Nos.22071073,21772218 and 21821002);the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000);State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences and Central China Normal University(CCNU).

摘　　要：A new set of stereochemically diverse phosphino-oxazoline ligands derived from simple L-amino acids and 2-(diphenylphosphaneyl)-benzoic acid were developed.Those mono anionic tridentated N,N,P-ligands promote the Cu-catalyzed enantioselective radical cou-pling of terminal alkynes with a broad range of benzylic halides including benzo-fused cyclicα-halides andα-silyl benzyl halides in high yield and excellent enantioselectivity under mild reaction conditions.With multi distinct sites for structural modification,a di-verse pool of chiral N,N,P-ligands is readily accessed,allowing for rapid optimization of the ligand structure for a specific substrate.Notably,the enantioselective alkynlylation of benzylic halides bonds in benzo-cyclic molecules has also been realized for the first time.

关 键 词：Copper catalysis Phosphino-oxazoline ligands CROSS-COUPLING Benzylic halides ALKYNES 

分 类 号：O62[理学—有机化学]