Rhodium-Catalyzed Pyridine-Assisted C-H Arylation for the Synthesis of Planar Chiral Ferrocenes  

作　　者：Chen-Xu Liu Zhong-Jian Cai Qiang Wang Zhi-Jie Wu Qing Gu Shu-Li You 

机构地区：[1]State Key Laboratory of Organometallic Chemistry,Center for Excellence in Molecular Synthesis,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,Shanghai 200032

出　　处：《CCS Chemistry》2020年第6期642-651,共10页中国化学会会刊（英文）

基　　金：the National Key R&D Program of China(2016YFA0202900),NSFC(21821002,91856201);the CAS(XDB20000000,QYZDY-SSW-SLH012)Science and Technology Commission of Shanghai Municipality(18JC1411302)。

摘　　要：Planar chiral ferrocenes are widely applied in organic synthesis,materials science,and medicinal chemistry,but their synthesis is not trivial.Herein,a highly efficient synthesis of planar chiral ferrocene-based pyridine derivatives via Rh(I)-catalyzed direct coupling of pyridylferrocenes with aryl halides was developed.Good yields and excellent enantioselectivity(95–>99%ee)are obtained for a wide range of substrates.The compatibility of gram-scale synthesis and relatively low catalyst loading(down to 1 mol%based on[Rh])enhance the practicality of the current method.The generated coupling products can be readily transformed into chiral ligands.Mechanistic studies suggest that the C–H bond cleavage of pyridylferrocene may be a reversible step and not the rate-determining step.Significant nonlinear effects indicate the existence of multiple metals or ligands in the active catalyst.

关 键 词：asymmetric catalysis C–H arylation FERROCENE planar chirality PYRIDINE 

分 类 号：O62[理学—有机化学]