Construction of Planar Chiral Ferrocenes by Cobalt-Catalyzed Enantioselective C–H Acyloxylation Enabled by Dual Ligands  

作　　者：Fan-Rui Huang Peng Zhang Qi-Jun Yao Bing-Feng Shi 

机构地区：[1]Center of Chemistry for Frontier Technologies,Department of Chemistry,Zhejiang University,Hangzhou 310027 [2]College of Material,Chemistry and Chemical Engineering,Key Laboratory of Organosilicon Chemistry and Material Technology,Ministry of Education,Hangzhou Normal University,Hangzhou 311121

出　　处：《CCS Chemistry》2024年第11期2783-2793,共11页中国化学会会刊（英文）

基　　金：supported by the National Key R&D Program of China(grant nos.2021YFF0701603 and 2022YFA1504302);the National Natural Science Foundation of China(grant nos.21925109,U22A20388,and 92256302);the Fundamental Research Funds for the Central Universities(grant nos.226-2023-00115 and 226-2022-00224);the College of Material Chemistry and Chemical Engineering,Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,Hangzhou Normal University(grant no.KFJJ2023003).

摘　　要：Oxy-substituted planar chiral ferrocenes are of great importance in asymmetric synthesis and pharmaceuticals.However,enantioselective C–H activation of ferrocenes that form C–O bonds remains a huge challenge and has not yet been reported.Herein,the asymmetric synthesis of oxy-substituted planar chiral ferrocenes is achieved by cobalt-catalyzed enantioselective dehydrogenative C–H acyloxylation.The use of a dual-ligand system consisting of a chiral salicyloxazoline(Salox)ligand and a neutral phosphine oxide ligand,which is oxidized in situ from the corresponding phosphine,resulted in good yield(up to 83%)and excellent enantioselectivity(90–99%ee).The utility of this unprecedented protocol is highlighted by its versatile synthetic transformations.

关 键 词：C–H acyloxylation COBALT dehydrogenative coupling ENANTIOSELECTIVITY FERROCENES 

分 类 号：O62[理学—有机化学]