Synergistic asymmetric diarylation of tethered alkenes via C–H functionalization of simple(hetero)arenes  

作　　者：Jian Yao Can Zhao Lili Shao Xiaohong Huo Xiaoming Wang 

机构地区：[1]Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs,Frontiers Science Center for Transformative Molecules,School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China [2]State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis,Center for Excellence in Molecular Synthesis,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China [3]School of Chemistry and Materials Science,Hangzhou Institute for Advanced Study,University of Chinese Academy of Sciences,Hangzhou 310024,China

出　　处：《Science China Chemistry》2024年第8期2710-2718,共9页中国科学（化学英文版）

基　　金：supported by the National Key R&D Program of China (2021YFA1500100);the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0610000);the National Natural Science Foundation of China (92256303, 22171278, 21821002);the Shanghai Science and Technology Committee (23ZR1482400);the Natural Science Foundation of Ningbo (2023J034)。

摘　　要：By virtue of the atom-and step-economy, utilization of simple arenes as a supplant of pre-prepared aryl metal species or aryl halides for the synthesis of arylated chiral molecules has attracted great attention from the synthetic community. While transition-metal-catalyzed enantioselective diarylation of tethered alkenes has been employed to prepare important chiral cyclic compounds, the direct use of simple arenes as aryl precursors is still underdeveloped, probably due to the difficulties in the effective control of the reactivity, site-selectivity and/or enantioselectivity. Herein we report an asymmetric Pd/Ag dual metal catalytic system for the non-directed, site-and enantioselective domino Heck/intermolecular C–H functionalization of arenes.Mechanistic studies showed that Pd and Ag act in cooperation in the catalysis and the chiral bisphosphine ligand plays a bifunctional role, i.e., assisting the silver species in the cleavage of the aryl C–H bond, while inducing the enantioselectivity on direct complexation with palladium. This method provides an efficient approach to the corresponding chiral oxindoles with good enantiomeric excesses from a broad scope of arenes, including fluoroarenes, heteroarenes and several complex products derived from medicines or natural products.

关 键 词：asymmetric Pd/Ag dual metal catalytic system simple arenes C–H functionalization bifunctional role chiral oxindoles 

分 类 号：O621.251[理学—有机化学]