Low-cost Metals Catalyzed C-O, C-N Bond Formation Reactions

The formation of heteroatomic compounds is an important area of research in organic synthetic chemistry and heteroatomic compounds are important structural motifs in either biologically or pharmaceutically active products or natural products.During the past decades,formations of carbon-heteroatom bond have gained much attention of organic synthesis chemists,and have encouraged the development of many synthetic strategies to prepare these compounds.However,the methods mainly depend on precious metals such as palladium,rhodium and iridium as catalysts,we are also interested in this research.Basing on the pioneering works in the formations of C-O,C-N bond,we wish to disclose our recent development on their further applications in synthetic organic chemistry.This dissertation is divided into three chapters:Chapter one is about iron-catalyzed esterification reaction of benzyl C-H bond.The esterification reactions of benzoylformic acids with alkylbenzene can be performed in the Fe F₃/DTBP catalyst system,and the product of target is obtained.This protocol has the characteristics of high efficiency,wide functional group tolerance,transition metal free conditions,etc.In addition,the reaction mechanism is also studied.The result provides indirect evidence that the reactions could have proceeded through a radical pathway.Chapter two is about synthesis of diphenylamines and triphenylamines via selective ring-opening arylations of benzoxazoles with aryl iodides.Diphenylamines products and triphenylamines products can be obtained via selective cleavage of the benzoxazoles with aryl iodides reaction in the presence of FeSO₄.7H₂O/Cs₂CO₃ and CuCN/Cs₂CO₃ catalytic systems respectively.Chapter three is about copper-catalyzed esterification reaction of benzyl halogenated hydrocarbons with acetylene acids.In this part,an efficient and practical method for esterification reactions of benzyl halogenated hydrocarbon with acetylene acids can be performed in the Cu I/Cs₂CO₃ catalyst system.With the advantages of high yield,utilizing inexpensive and low toxic catalyst,this protocol is suitable for all kinds of carboxylic acid compounds.