Direct Synthesis Of Thioamides And Its Dirivertives Based On The Strategy Of I₂-promoted C-H Bond Functionalization

In recent years,the functionalization of organic compunds has emerged as one of the most extensive and atrractive reaction strategy for chemists.Due to its high bond energy(413 kJ/mol),the C-H bond exists in variety of organic molecules and performed few reactions.However,it is significant to directly finish the C-H bond to C-hetero bond(functionalization)in many fields:In nature,it is the main trasformation of metabolism.In industry,it is the cole procedure of medicine production,fine chemicals,and energy access.Consequently,people have payed a lot of attention in the field of C-H bond functionalization.So far,there have been a large number of reports about C-H bond functionalization,and transition metal,organic molecules have played the main role of promoting the C-H bond functionalization by reagents.In addition,inorganic nonmetal active reagents have revealed their catalytic property in the field of C-H bond functionalization.These reagents provide important theoretical basis and reference for chemists to discover new methods to synthesize multi-functionalized organic molecules.On the guiding ideology of C-H bond functionalization,in this dissertation,we have mainly investigated the direct construction of a-ketothioamides and thiobenzamides via the stratege of C-H bond functionalization from aryl methyl ketones and benzylamine under the promotion of iodine.The main content was as follows:In chapter 1,we firstly summarized the reaction type of C-H bond functionalization in organic synthesis.Then the synthetic methods of thioamides were overviewed.The research topic was put forward on this basis.In chapter 2,based on the strategy of C-H bond functionalization,the iodine was utilized as reaction media and the a-ketothioamides were selected as the target molecule.Available methyl ketones,morpholine,and aniline were used as substrates,and sodium hydrosulfidc was chosen as the source of sulfur.We employ iodine to activate the hydrocarbon bond which located on the ortho of carbonyl.We successfully finished the functional construction of a-ketothioamides via several unit reactions:iodination/substitution,Komblum oxidation,and condensation.In chapter 3,based on the activation of iodine for C-H bond functionalization,we employed benzylamines as the starting substrates and sodium hydrosulfide as the source of sulfur.We successfully finished the effectively one pot construction of thiobenzamides under the reaction system of I2/DMSO via several unit reactions such as oxidation and condensation.