Catalytic Three-component Cross-coupling Reaction Of Halogenated Compounds, Carbon Monoxide And Arylboronic Acid Under Normal Pressure

Diarylmethanone and diarylethanone compounds are two important kinds of organic intermediates,which have attracted great attentions in organic synthetic chemistry.However,a versatile,efficient,environmentally friendly and inexpensive preparation method using metal or metal-free catalyst has not been reported yet.Our work mainly includes three parts:(1)the development of nickel catalyzed carbonylative Suzuki coupling reaction under atmospheric pressure in green solvent to synthesize diarylmethanone.(2)the development of iron catalyzed carbonylation of arylhalides with arylboronic acids under an atmosphere of carbon monoxide.(3)the development of metal-free catalyzed carbonylative coupling reactions of benzyl chlorides with arylboronic acids under an atmosphere of carbon monoxide.Our main research results are summarized as follows:1.We have developed nickel catalyzed carbonylation of arylboronic acid with aryl iodide to synthesize diarylmethanone.Under the model reaction of 4-nitro-iodobenzene and phenylboronic acid,we optimized acid,base,solvent,and catalyst.By using NiCl2 as the catalyst,pivalic acid(PivOH)as the acid,K3PO4 as the base,and polyethylene glycol-400 as the solvent,we obtained the optimum result.Under the optimized conditions,arylboronic acids and aryl iodides were extended respectively,most of which resulted in over 80%yields.Transmission electron microscopy(TEM)analysis indicated that nickel nanoparticles were in situ generated.We also investigated the recyclability of the in situ nanocatalysis system,which indicated that the reaction still gave up to 85%yield in the 5th cycle.2.We have developed iron catalyzed carbonylation of aryl halides with aryl boronic acids under an atmosphere of carbon monoxide.Under the model reaction of 4-nitro-iodobenzene and phenylboronic acid,we optimized the base,solvent and catalyst.By using FeCl2(4 mol%)and FeCl3(6 mol%)as the catalyst,NaHCO3 as the base and polyethylene glycol-400 as the solvent,we obtained the optimum result.3.Under the optimized condition,arylboronic acids and aryl iodides were extended respectively to synthesize a series of diarylmethanones and the preliminary study of the reaction mechanism has been dscribed.4.We demonstrated a metal-free catalyzed carbonylation of benzyl chloride,arylboronic acid to synthesize diarylethanone analogues.Under the model reaction of 4-fluorobenzyl chloride and phenylboronic acid,we optimized the base,solvent and catalyst.By using Nal as the catalyst,Na3PO4(4 equiv)and K2HPO4(O.lequiv)as the base and polyethylene glycol-400 as the solvent,we obtained the optimum result.Under the optimized conditions,the reactants arylboronic acids and benzyl chlorides was extended respectively to synthesize a series of diarylethanone.We also proceeded a preliminary study of the reaction mechanism.