Rhodium-catalyzed Ring-opening Reaction Of Cyclopropanol Compounds And Asymmetric Alkylation Of Aromatic Hydrocarbons

The transition metal-catalyzed C-H/C-C functionalization strategy has provided a straightforward and atom-economical approach compared with traditional functional group conversion strategies.It represents a simple and efficient method for the synthesis of pharmaceutical intermediates,natural products and polymer compounds.Cp*Rh(?)is widely used in metal catalytic systems due to easy preparation,high efficiency,controllable site selectivity,and good compatibility of substrates and functional groups.In recent years,as several types of Cp? ligands have been applied to transition metalcatalyzed asymmetric C-H bond activation,the research on Rh(?)-catalyzed enantioselective conversion has achieved rapid development.This paper mainly studies the Cp*Rh(?)-catalyzed ring-opening functionalization reaction of cyclopropanol compounds and chiral Cp?Rh(?)-catalyzed asymmetric synthesis of central chiral compound.The specific research contents are as follows:1)Rh(?)-catalyzed ring-opening amidation and alkylation of cyclopropanols have been realized for mild and efficient synthesis of diverse ?-functionalized ketones by integrating C-C activation and ?-insertion of nitrenes and carbenes,where readily available 1,4,2-dioxazol-5-ones and diazo compounds serve as the nitrene/carbene precursor with water as the solvent and nitrogen or CO2 as the byproduct.The current protocol features environmental friendliness,functional group compatibility,additivefree conditions,and high atom/step-economy.2)Using chiral Cp?Rh(?)as a catalyst,the asymmetric alkylation reaction of N(tert-butyl)benzamide and ?,? unsaturated ketone was realized.The ?-aryl ketone compound was synthesized under mild conditions and good enantioselectivity with a broad substrate scope.