Study On The Synthesis Of α,β-unsaturated Ketones By Palladium And Iron-catalyzed Suzuki Coupling Reaction Of Carbonylation At Atmospheric Pressure

α,β-unsaturated ketones are an important kind of pharmaceutical organic intermediates,which have become an important and active topic in the field of organic chemistry.However,a highly efficient,environmentally friendly metal-catalyzed carbonylation Suzuki coupling reaction for the synthesis ofα,β-unsaturated ketones has not been reported yet.Our work mainly includes three parts:(1)the development of ligand-free Pd-catalyzed carbonylative Suzuki reaction with vinylboronic acid under atmospheric pressure of carbon monoxide and at room temperature in green solvent to synthesize α,β-unsaturated ketones.(2)the development of ligand-free Pd-catalyzed carbonylative Suzuki reaction with vinyl iodide under atmospheric pressure of carbon monoxide and at room temperature.(3)the development of iron-catalyzed carbonylative Suzuki reaction with vinylboronic acid under atmospheric pressure of carbon monoxide.Our primary research results are summarized as follows:1.A ligand-free Pd-catalyzed carbonylative Suzuki reaction with alkenyl boronic acid to α,β-unsaturated ketones under atmospheric pressure of carbon monoxide and at room temperature has been demonstrated.Under the model reaction of 4-nitro-iodobenzene and trans-β-styrylboronic acid,we optimized catalyst,base,acid and solvent.By using Pd(OAc)2 as the catalyst,NaHCO3 as the base,pivalic acid(PivOH)as the acid,polyethylene glycol-400 as the solvent,under atmospheric pressure of carbon monoxide and at room temperature,we obtained the optimum result.Under the optimized conditions,aryl iodides and alkenyl boronic acids were extended respectively,most of which resulted in over 80%yields.We also proceeded a preliminary study of the mechanism.2.A ligand-free Pd-catalyzed carbonylative Suzuki reaction with alkenyl iodide to α,β-unsaturated ketones under atmospheric pressure of carbon monoxide and at room temperature has been demonstrated.Under the model reaction of phenylboronic acid and trans-β-4-methoxystyryl iodide,we optimized catalyst,base and solvent.By using Pd(OAc)2 as the catalyst,NaHCO3 as the base,polyethylene glycol-400 as the solvent,under atmospheric pressure of carbon monoxide and at room temperature,we obtained the optimum result.Under the optimized conditions,alkenyl iodide and phenylboronic acid were extended respectively,most of which resulted in over 80%yields.We also proceeded a preliminary study of the mechanism.3.A ligand-free Fe-catalyzed carbonylative Suzuki reaction with alkenylboronic acid to α,β-unsaturated ketones under atmospheric pressure of carbon monoxide has been demonstrated.Under the model reaction of 4-nitro-iodobenzene and trans-β-styrylboronic acid,we optimized catalyst,base and solvent.By using FeCl2 as the catalyst,NaHCO3 as the base,polyethylene glycol-400 as the solvent,at 100℃,we obtained the optimum result.Under the optimized conditions,aryl iodides and alkenylboronic acids were extended respectively,most of which resulted in over 80%yields.We also proceeded a preliminary study of the mechanism.