Study Of Au(â… ) Catalyzed Hydroarylation Reaction Of Alkynes And Mo(â…¥) Catalyzed Oxidation Reaction Of Amines

In recent years, researches on organic reactions catalyzed by gold(I) complex have been developed rapidly, so gold(I) complex becomes a potential emerging field of research. Up to date, gold(I) complex has been used as the catalyst of N-alkylation reaction, C-C coupling reaction, redox reaction, etc. successfully and has made significant breakthrough in these field. It has considerable significance to explore new reactions catalyzed by Ph3AuCl in consideration of that Ph3AuCl shows strong catalytic activity under mild conditions. To be the same with gold(I), Mo(VI)complex is also a very important organic-metal catalyst. Until now, molybdenum dioxo-complexes has been used in epoxidation and ring opening, Pinacol coupling reactions, redox reaction, rearrangement reaction and nucleophilic reaction etc. It is of considerable significance to study the organic reactions catalyzed by molybdenum dioxo-complexes according to its wide range of catalytic activity. Three parts are included in this thesis:Part 1 Hydroarylation reaction of alkynes with heteroarenes catalyzed by Pb3AuClThe synthesis of functionalized heteroarenes continues to attract considerable attention due to their importance in organic chemistry and our daily life. Recently, transition metal catalysts such as Ru, Rh, Pt, Pd and In catalyzed hydroarylation reaction of alkynes and heteroarenes is considered to be one of the most efficient method. However, all of these catalysts have several disadvantages. To our own knowledge, these reactions catalyzed by homogenous gold(I) complex were scarely reported. Firstly, the catalyst was prepared and the feasibility of the hydroarylation reaction of alkynes with 1-methylpyrrole using a catalyst system consisting of Ph3PAuCl in CICH2CH2Cl was discussed. Influences of solvent, temperature, catalyst amount, ratio of catalyst and additive and the ratio of the two substrates are studied to screen out the optimal conditions. Then the scope of alkynes and pyrroles are extended under the optimal conditions. The experimental results indicate that both aromatic alkynes and aliphatic alkynes can react with 1-methylpyrrole to afford desired product. Electron-withdrawing groups have strong negative effect on the reaction activity of heteroarenes, though electron-withdrawing groups on alkynes have little effect on the yield of the products.Part two oxidation of benzylamine catalyzed by MoO2(acac)2The synthesis of oxime attract considerable attention due to their importance in organic chemistry. Many alternative methods exist for the synthesis of oximes, but all of these methods are have some drawbacks and limitations. To our own knowledge, there is no reports on synthesis of oxime by oxidation of benzylamine catalyzed by Mo(VI) complexes. In this paper, the feasibility of the oxidation reaction of benzylamine using MoO2(acac)2 as catalyst and TBHP as oxidant in toluene was discussed. Influences of solvent, temperature, catalyst amount and oxidant amount are studied to screen out the optimal conditions. Then the scope of amines are extended under the optimal conditions. The experimental results indicate that amines can be oxidized to oxime catalyzed by MoO2(acac)2 directly and have strong reactivity.