Carbon–Carbon And Carbon–Heteroatom Bond Formation Via Transition Metal Promoted C–H Activation

Transition metal-promoted direct C–H bond functionalization is a simple,efficient and atomic-economy synthetic strategy.In recent years,the research of transition metal-promoted C–H bonds activation has developed rapidly.Transition metal-promoted direct C–H bond activation to form C–C bonds,C–Het bonds which are widely present in organic molecules has become an important research area.This paper has developed the reactions of transition metal-promoted direct C–H bond activation to consturct C–S bond and heterocycles.Ir/Cu-catalyzed C–H bond activation to construct C–C bond,C–O bond and heterocycles:In this work,we employed the carboxyl group as a directing group and oxygen source to achieve Ir/Cu-catalyzed oxidative C–H/O–H annulation.We used simple-structure and easily-obtained aromatic acids and saturated ketones as starting substrates,obtaining3-substituted phthalides through the combination of copper-catalyzed saturated ketones dehydrogenation and iridium-catalyzed oxidative annulation between benzoic acids and unsaturated ketones in one-pot reaction.This method is suitable for a wide range of substrates and shows good functional group compatibility.This strategy affords a feasible strategy to obtain diverse five-membered heterocyclic phthalide derivatives.Cu/Ag-promoted C–H bond activation to construct C–S bond with Bunte salts as sulfur reagents: In this work,we have developed Cu/Ag-promoted C–H bond activation to synthesis2-thio-substituted azoles with Bunte salts as sulfur reagents which avoided undesirable odor and air-sensitive thiol,disulfides compounds.Silver salt could coordinate with the nitrogen atom of azoles to increase the activity of C2–H bond.This method shows good functional group tolerance,and thiazoles with sensitive ester and aldehyde functional groups also could process well.This strategy affords a simple and efficient way to furnish 2-thio-substituted azoles.