Transition Metal-catalyzed C-N And C-C Cross-coupling Reactions Of Di(hetero)aryl Disulfides

Recently,transition metal catalyzed cross-coupling reaction has become a powerful and indispensable tool for the construction of C-C,C-N bonds etc in synthetic organic chemistry.The most common electrophile of these coupling reaction are halides and trifluomethanesulfonate.Electrophilic reagents of these coupling reaction showed a high reactivity,selectivity,and unique advantages.Howere,organic halides are harmful to the environment,generate a lot of halogen-containing by-products after the reaction finish,difficult to prepare and trifluoromethanesulfonic acid ester is not stable in water.Consequently,the search for alternative electrophiles as novel substrates to organic halides for the cross-coupling reactions has been the focus of much attention.At present,disulfides,as interesting electrophiles,have been caused increasing attention in modern cross-coupling reactions.Compared with aryl halides disulfides have its own advantages.For example,the disulfides are always easily available and steable.The development of cross-coupling reaction for disulfides are not only a supplement to the existing system,but can overcome difficulties for other cross-couplsssing reactions.This thesis reviewed the recent advances of disulfides involved cross-coupling reactions.The C-N,C-C coupling reactions under different conditions between di?hetero?aryl disulfides and aromatic,oxazoles,thiazoles have been tested successfully.Meanwhile,a series of multisubstituted pyrimidine derivatives were synthesized,which provides a novel protocol for synthesizing and modifying pyrimidine derivatives.The main research contents and results were as follows:1.We developed an efficient method for C-N bond formation through the cross-coupling of disulfides with anilines and aliphatic amines under ligand-free conditions involving the cleavage of the C-S bond of 1,2-di?pyrimidin-2-yl?disulfides.2.We developed an efficient method for C-N bond formation through the cross-coupling of disulfides with N-heterocycles under ligand-free conditions involving the cleavage of the C-S bond of 1,2-di?pyrimidin-2-yl?disulfides.3.We developed an efficient method to construct C-C bond via direct C-H functionalization of oxazoles or thiazoles with C-S bond cleavage of di?hetero?aryl disulfides.All products were confirmed by ¹H NMR,¹³C NMR and HRMS spectroscopic analysis.