Study On The Hydroacylation And Hydrophosphine Acylation Of C(sp~2)-H Bond Mediated By Visible Light

α-Keto acids are a specialized form of carboxylic acid derivatives with multiple active groups that serve as an important intermediate interact with a variety of reagents in organic synthesis.Their active chemical properties and ease of decarboxylation make them an ideal acyl source for the construction of acyl carbon-carbon bonds and acyl carbon-hetero bonds in the reaction.Consequently,a series of reactions involvingα-keto acids have attracted wide attention.In recent years,the decarboxylation ofα-keto acids through transition metal oxidation has been widely revealed.However,the decarboxylation mediated by visible light under mild condition rarely reported.Organophosphine compounds have significant applications used in material science and pharmaceutical fields,serving as the most commonly ligands and catalysts in organic synthetic chemistry.Therefore,the synthesis of organophosphine compounds has attracted extensive attention of chemists.So far,the reported methods for constructing phosphine-containing compounds are mainly realized by transition metal catalysis,and there are few examples reported by visible light-mediated under mild conditions.This paper mainly realizes the hydroacylation and hydrophosphonylation of C(sp~2)-H bond under mild conditions through visible light mediation.The work of this paper mainly includes the following two aspects:(1)Visible light promoted the decarboxylhydroacylation of quinones withα-keto acids.Hydroacylation of benzoquinones/naphthoquinones were efficiently achieved under visible light irradiation without the addition of photosensitizer.The reaction proceeded smoothly at room temperature and a series of 2,5-dihydroxyketones were synthesized.In this reaction system,both aryl keto acids and alkyl keto acids can react smoothly and the corresponding hydroacylation products can be obtained in moderate to good yield.(2)For the first time,a series of phosphine oxycompounds were synthesized by hydrophosphine acylation involving bimolecular alkenes mediated by alkyl radicals.The reaction has the advantages of mild conditions and wide-rangeing of substrates.Additionally,the obtained synthesized oxygen compound can be converted into the corresponding phosphorus ligand during later stage,expanding the repertoire of phosphorus ligand types.