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...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.展开更多
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)+1 种基金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).
文摘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.
