Research On Dual Photoredox And Nickel Catalyzed Insertion Of Alkenyl Bromides Into Alkyne

1,3-Dienes are versatile building blocks for numerous valuable transformations and important structural motifs present in medicinally active natural products,pharmaceuticals,and agrochemicals.Therefore,the development of efficient methodologies for their synthesis has attracted an increasing research interest in the past decades.Among several elegant catalytic methods,represented by vinyl-vinyl cross-couplings,alkyne-alkyne cross-couplings,and carbofunctionalization of alkynes have been successfully developed to yield 1,3-dienes with high efficiency.Nevertheless,most of these methods are generally delivering the hydrogenated 1,3-dienes.the synthesis of functionalised conjugated dienes such as halogenated 1,3-dienes remains underexplored.We have developed an efficient,redox-neutral,and atom economical protocol via photoredox and nickel dual catalysis.We have achieved intermolecular regioselective 1,2-addition of alkenyl bromides to alkynes to afford a series of bromo-functionalized 1,3-diene products in one step with moderate to good yields in the present of Ir[d F（CF₃）（ppy）₂]（dtbbpy）PF₆ as photoredox catalyst,Ni Br₂·diglyme as nickel catalyst,（4S,4S’）-2,2’-（propane-2,2-diyl）bis（4-benzyl-4,5-dihydrooxazole）（Bn-BOX）as ligand,and diisopropylamine（DIPA）as base.The reaction domenstrates broad substrate scope and good functional group tolerance,offering a generic and complementary strategy to realize difunctionalization of alkyne.