Research On Copper Catalyzed Synthesis Of Peresters And One Pot Synthesis Of Allylic Esters

In recent years, peresters and allylic ester compounds draw much attention because of their various applications, and there are a variety of methods reported for the synthesis of these kinds of compounds. However, most of them suffer from shortcomings such as harsh reaction conditions, poor functional tolerance and substrate scope. Considering the concept of green chemistry, seeking for an environmental friendly carbon-carbon and carbon heteroatom bond constructing method draw many interests of researchers. Meanwhile, C-H activation has received the widespread attention in the field of organic synthesis because of its high atom economy and less pollution. Thus, it should be of great research value to synthese peresters and allylic ester compounds via C-H activation of aldehydes, which provides a new synthetic method to prepare these compounds.A highly efficient copper catalyzed synthesis of peresters from aldehyde is developed. Further more,an one-pot synthesis of allylic esters was also achieved.(1)Cu(I) complexes catalyzed synthesis of peresters with aldehyde as the substrateWith the promotion of bpy ligand, moderate to excellent yield of peresters were achieved by using Cu I as catalyst and aldehydes as substrates, under a mild, neat condition. Compared with previous reports in literatures, the new methodology significantly shortened the reaction time and showed better functional group tolerance and substrate scope.(2) Cu(I) complexes catalyzed one pot synthesis of allylic estersWithout additional catalyst, cyclohexene was then added to the reaction mixture of the copper catalysted reaction above, and allylic esters were obtained after heating the mixture for anther 6~18h. Compared with the previous reports, allylic esters were prepared with much shorter time under a neat condition, and good yields were also achieved. To our best of knowledge, this is also the first report on copper catalyzed one-pot synthesis of allyllic ester compounds.Following the two procedures above, thirteen different kinds of peresters and twelve kinds of allylic esters were synthesized and characterized successfully.