Study On The C-S Bond Formation Under Metal-free Conditions

The sulfur-containing organic compounds are important structural units of physiologically active molecules. Therefore, the effective construction of C-S bonds plays an important role in organic synthesis. In this paper, the formation of sulfur ylide and its [2, 3] -?rearrangement reaction were carried out by using dipotassium hydrogen phosphate as additive, and a series of ?-acylglyceryl sulfide compounds with important application value were constructed. The main contents of this thesis include the following parts,:Chapter 1. The research progress of sulfur ylide [2, 3]-sigma rearrangement reaction. In this chapter, the literatures were reviewed in this part, and the progress of the research on the reaction of diazonium compounds and thioethers with different types of transition metals was analyzed. The advantages and disadvantages of the literatures are summarized.Chapter 2. The research methods of constructing a-carbonyl substituted homoallylic sulfides by Doyle-Kirmse reaction under transition-metal-free conditions. In this chapter, the Doyle-Kirmse reaction of a-bromocarbonyl compounds with allyl sulfides was achieved by the promotion of dipotassium hydrogen phosphate, which synthesized a variety of a-carbonyl substituted homoallylic sulfide compounds. The reaction conditions with broad substrates tolerance were relatively mild.Chapter 3. The synthesis of a-carbonyl substituted homoallylic sulfides compounds using one-pot method. This chapter further simplified the former metal-free Doyle-Kinnse reaction. With frequently-used base K2HP04 as the additive, the thiol, allyl bromide and a-bromocarbonyl compounds were used as starting materials, the construction of C-S bond was achieved under transition-metal-free with the one-pot method, which offered a green and simple synthetic system.Chapter 4. Study on the synthesis of polyallyl sulfide compounds.Based on the former multiple component one-pot reactions, we used tert-butyl mercaptan or diallyl sulfide as the substrate to synthesized?-carbonyl substituted homoallylic sulfides compounds. Under this mild conditions, the four centered-carbon compouds and a-carbonyl substituted homoallylic sulfides compounds can also be obtained with the method of [2, 3]-sigma rearrangement reaction.