Ruthenium-Catalyzed C(sp~2)-F/C(aryl)-H Cross-Coupling Reaction To Synthesize Tertiary Phosphine

Due to their special properties,organofluorine compounds have an important effect on the fields of material science,medicine,and synthetic organic chemistry.From the perspective of efficiently developing organofluorine compounds,not only C-F bond formation but also various cross-coupling reactions involving C-F bonds have become the subject of current active research.Compared with the two,although some progress has been made in the specific research field of functional group conversion of C-F bonds,various cross-coupling reactions involving C-F bonds still need to be developed.Due to the high bond dissociation energy of the C–F bond,the selective defluorination functionalization of fluorine-containing compounds is lagging and still quite challenging.In this paper,the C(sp~2)-F/C(aryl)-H cross-coupling reaction to synthesize alkenyl phosphine compounds and alkyl tertiary phosphine compounds based on ruthenium-catalyzed tertiary phosphine-assisted CH activation strategy,and ruthenium-catalyzed tertiary phosphine-assisted hydrogen Synthesis of C-8 alkyl naphthalene phosphine compound by arylation reaction.1.Ruthenium-catalyzed C(sp~2)-F/C(aryl)-H cross-coupling reaction to synthesize alkenylphosphine compoundsUsing ruthenium catalysis and a phosphine-directed system,the C(sp~2)-F/C(aryl)-H cross-coupling reaction of inert monofluoroalkenes was achieved for the first time,and a series of biarylphosphinoene ligands were synthesized.The product of the catalytic system has good chemoselectivity and stereoselectivity,good functional group tolerance and excellent yield.As a ligand in the palladium-catalyzed allylation reaction,it can improve the activity of the catalyst.The significance and utility of this system lies in the fact that,under the condition of low catalyst loading,the alkenyl product used as a ligand exhibits better catalytic effect than other commercial tertiary phosphine ligands.This method has certain guiding significance for the later modification of tertiary phosphine compounds and the synthesis of phosphine ligands.2.Ruthenium-catalyzed tertiary phosphine-assisted hydroarylation to synthesize C-8 alkylnaphthalene phosphinesWe have developed a ruthenium-catalyzed tertiary phosphine-directed C-8alkylation of the naphthalene ring,providing a method that can directly obtain alkyl-containing naphthine phosphine ligands.Mechanistic experiments show that acidic ligands play an indispensable role in this reaction.The reaction system has mild conditions,a wide variety of substrates,and a variety of polycyclic aromatic hydrocarbons can be well reacted.In addition,the C-8 alkylation product was confirmed to reduce the loading of palladium catalyst to 100 mol ppm in the palladium-catalyzed suzuki coupling of alkylboronic acids.Compared with some commercial tertiary phosphine ligands,our synthesized alkylated naphthylphosphine ligands perform better as reaction ligands.3.Ruthenium-catalyzed C(sp~2)-F/C(aryl)-H cross-coupling tandem hydrogenation reduction synthesis of alkyl phosphine compoundsWe developed a ruthenium-catalyzed C(sp~2)-F/C(aryl)-H cross-coupling tandem method to synthesize alkylphosphine compounds by hydrogen reduction.The method is well tolerated by functional groups and has excellent yields.The brominatednaphthyl tertiary phosphine substrate can react well,leaving an important reaction site for the subsequent modification of the naphthyl tertiary phosphine ligand,leavingmore possibilities.This work not only enriches the phosphine ligand library,but also provides a new strategy for the formation of tertiary phosphine compounds.