Copper-catalyzed C-P(?) Bond Formation Reaction With Acylphosphine As Phosphorus Source

Phosphine ligands represented by triarylphosphines are an important part of the organophosphorus compound.With the development of coordination chemistry,the development of phosphine ligands has been greatly promoted,especially in homogeneous catalytic reactions.The greatest advantage of phosphine ligands is their unique electronic and steric properties,which can effectively control the reactivity and chemoselectivity of coordination metal centers.Therefore,the development of efficient and economical methods for constructing C-P bonds has been receiving much attention.In this paper,we mainly introduce a method for directly constructing C-P(III)bond by transition metal catalysis.This paper is divided into two parts.:One:copper-catalyzed the coupling reaction of acylphosphine as trivalent phosphorus source and aromatic iodide.The optimal reaction conditions were obtained by reacting p-methylbenzoyl diphenylphosphine and iodobenzene as model substrates.The isolated yield was up to 94%.Under the optimal reaction conditions,33 aryl iodides and 4 aryl bromide were investigated.Finally achieving the synthesis of the corresponding triarylphosphines compound in a yield of 25%-99%;by knowing the applicability of the substrate,whether the aromatic iodide is connected to electron donating or electron withdrawing Groups,even for a variety of potentially easily convertible functional groupsTwo:It is precisely because of the aryl iodide coupling reaction system that the aryl bromide with electron-withdrawing substituent has a certain conversion effect.Therefore,the optimal reaction conditions were obtained by reacting p-methylbenzoyl diphenylphosphine and 1-bromonaphthalene as model substrates in DMEDA as ligand.Under optimal conditions,the optimal reaction conditions were obtained,and the isolated yield was up to 65%.Under the optimal conditions,the substrate suitability of 9 aryl bromides was investigated,and finally obtained in 22%-83%isolated yield.The target product;has certain compatibility with the functional group,and the electron-deficient aromatic bromide is more favorable for the reaction than the aromatic ring with richer electron cloud density.A classical dual-halogen monitoring experiment was used in the mechanism discussion to demonstrate the mechanism of the mechanism by monitoring the presence of single coupled products by nuclear magnetic resonance and the changes of single and double coupled products during the monitoring process.Through the analysis of the monitoring data,it is speculated that the reaction has undergone an oxidation addition-reduction elimination mechanism.