Synthesis Of Carbon/heterocyclic Compounds By Cascad Carbonylative Reaction Using CO Surrogates

As an important raw material of organic chemical industry,CO was neglected in the 18th century,until the British chemist Cruickshank confirmed the existence of CO in 1801.After Heck reported first that Pd-catalyzed carbonylative reaction in the 1970s,the development of the carbonylative reaction has advanced by leaps and bounds.After decades of development,the carbonylative reaction has provided direct and atomically economical method for CO to embed organic compounds.And because CO surrogates has the advantages of easy preparation,easy storage,low equipment requirements,safety,and economy,the carbonylative reaction using CO surrogates has become an advantageous method for synthesizing carbonyl compounds.On the other hand,cascade reactions can effectively synthesize carbon/heterocyclic compounds and have obvious advantages over economic methods,environmental protection,and short steps.Therefore,it is of great significance that the study of synthesizing carbon/heterocyclic compounds by using carbonylative cascade reactions using CO surrogates.In this paper,the carbon/heterocyclic compounds synthesized via cascade reaction of Pd-catalyzed carbonylation using CO surrogates.The works described is as follows:1.A cascade carbonylative reaction using TFBen as carbonyl source was achieved to synthesize benzodihydropyrones.Using 2-iodophenol,cinnamyl chloride as substrate,Pd(OAc)2 as catalyst,BuPAd2 as ligand,under mild reaction conditions,the reaction can obtain benzodihydropyrans in moderate to good yields.2.A cascade carbonylation reaction using formic acid as carbonyl source was achieved to synthesize cyclopentenone compounds.Using iodobenzene,3-hexyne compounds as substrate,Pd(acac)2 as catalyst,and Sphos as ligand,under mild reaction conditions,the reaction can obtain cyclopentenone compounds in moderate to good yields.3.A cascade carbonylation reaction with formic acid and acetic anhydride as carbonyl source was realized to synthesize imidazole compounds.Using trifluoroacetimide chloride,diphenyliodonium trifluoroacetate,propargylamine as the substrate,PdCl2 as the catalyst,and PPh3 as the ligand,the reaction can be obtained in very excellent yields under mild reaction conditions.Imidazole compounds,and the reaction has very good functional group compatibility and substrate applicability.