Access To Two Different Types Of Sulfides Through The Free Radical Reaction Of Vinyl Halides With Thiols

This thesis was concerned with the studies on the construction of C-S bond under free radical conditions. It mainly consists of the following two parts:In chapter 1, the reports about synthesis of alkyl and vinyl sulfides were concluded. The most common method for the synthesis of alkyl sulfides involved the substitution reaction of alkyl halides with thiols in the presence of a base. Other methods included the radical-mediated, acid-catalyzed, and metal-catalyzed hydrothiolation of alkenes. The methods of synthesizing vinyl sulfides included radical-mediated or metal-catalyzed hydrothiolation of alkynes, radical-mediated or transition metal-catalyzed coupling reaction of vinyl substitutes with various sulfides.In chapter 2, a highly chemoselective radical-mediated C-S bond forming reaction of vinyl halides with thiols by AIBN catalyzed is described, in which the corresponding alkyl or vinyl sulfides could be specifically formed from the vinyl iodide substrate in aprotic (toluene) or protic (MeOH) solvent, respectively. Vinyl bromide and vinyl chloride substrates provided vinyl sulfides as the sole product in both aprotic and protic solvents. The method provides a strategy for the divergent synthesis of sulfides with excellent selectivity and high efficiency, therefore providing an additional route for related synthesis of natural product, even to medicinal chemistry. At last, the mechanism of the reaction influenced by halides and solvent was discussed.