Investigation On The Multicomponent Reactions Of Aryne Precursors And Alkyl Halides With Carbon Dioxide

Carbon dioxide is regarded as an ideal C1 synthon by the advantages of being nontoxic,low-cost and abundant.The utilization of carbon dioxide to construct various high value-added products can not only turn the waste into treasure but also provide a potential strategy for solving the dramatic decreasing of fossil fuels.Though the recent years have witnessed significant progress about transformations of CO₂,it is still in a stagnant stage focusing on fundamental researches because the industrial CO₂transformations are remain in their infancy.Therefore,the exploitation of new methods for the transformation of CO₂,especially for the C-C bond formation,is still an appealing and challenging subject.Due to the thermodynamic stability and kinetic inertness of CO₂,the chemical transformation of CO₂ into carboxylic products in a mild reaction conditions is remain a great challenge.To accomplish the purpose,we utilized the high-energy aryne intermediate generated in situ to capture carbon dioxide into fine chemicals:（1）A three-phase four-component coupling reaction（3P-4CR）involving KCl,arynes,chloroalkanes and CO₂ has been reported.The reaction involves the formation of three different new C-Cl,C-C,and C-O bonds in a one-pot fashion,providing an operationally simple method for the synthesis of different types of o-chlorobenzoates.（2）We described a three-component coupling reaction of arynes,allyl/cinnamyl bromide and carbon dioxide.The reaction realizes the direct bromination-carboxylation of the benzyne for the first time and provides a new approach for the efficient synthesis of various o-bromobenzoates.Furthermore,the reaction is highlighted by its mild reaction conditions,wide substrate scope and good practicability.