Study Of N-alkylation Reaction Of Alcohols And The Nucleophilic Addition Reaction Of Phenyl Acetylene Catalyzed By Homogenous Gold Complex

In recent ten years, organic reactions with gold(I) complex have developed rapidly, so gold(I) catalyst becomes the most development potential of the emerging field of research. Gold(I) complex can be used to catalyze the C-C coupling reaction, REDOX reaction, C-H key activation reaction, etc. And it has made significant progress and breakthrough. Because Ph3PAuC1has strong catalytic activity and reaction condition with this catalyst is mild, it has considerable significance to explore new organic reactions witn Ph3PAuCl.Two parts are included in this thesis:Part1N-alkylation of alcohols and amines catalyzed by Ph3PAuClThe N-alkylation of amines with alcohols to produce nitrogen-containing compounds has been focused as a efficient method. Recently, many transition metal catalysts, such as Ru, Ag, Ir, Fe and Au0have been reported to be active for the N-alkylation. However, several disadvantages to these catalysts are as followed:(1) the reaction with Ru catalyst needs high temperature;(2) the reaction with Au0catalyst needs inert atmosphere (N2). In this paper, a homogeneous gold(I) complex was firstly reported to catalyze the N-alkylation of amines with alcohols for good selectivity without an inert atmosphere. Firstly, the catalyst Ph13PAUC1was prepared from gold chloride acid and used to catalyze direct reductive amination of benzaldehyde with Hantzsch ester. Then, the feasibility of the reaction with Ph13PAUC1was discussed in this section when benzyl alcohol and aniline were used as model substrates,t-BuOK as base,1,4-dioxane as solvent. And the influence of the solvent, reaction temperature, the type of base, amount of catalyst, cocatalyst, and reaction time on the yield of the product was explored. Lastly, the optimum reaction conditions were obtained. Under the optimum conditions, the scope of various amines and alcohols was extended in this section. The experimental results showed that aromatic compounds had higher reactivity than aliphatic compounds, and the electron-donor group compounds had higher reactivity than the electron-attractive group compounds. Finally, the catalytic mechanism for the reaction was also researched.Part2Addition reaction of acetylene and pyrrole derivatives catalyzed by PI13PAUC1Pyrrole derivatives containing functional groups play an important role in medicines, pesticides, spices, etc. These compounds can be synthesized in various methods. Recently, many transition metal catalysts, such as In、Pd、 Pt、 Ru have been reported to be active for the addition reaction of phenylacetylene and pyrrole derivatives. However, there are several disadvantages to these catalysts. For example, AcOH should be added to activate the Pt precatalyst in the double-hydroarylation reaction. This reaction with homogenous gold(I) complex was scarely reported. The addition reaction of phenylacetylene with N-methyl pyrrole using Ph3PAuC1as catalyst was discussed in this section and different reaction conditions were investigated such as cocatalyst, reaction solvent, temperature, the dosage of catalyst and cocatalyst for the reaction. The results showed that AgOTf was the most feasible cocatalyst. And the optimum reaction conditions were as follows:65℃of the reaction temperature,10mol%of catalyst and cocatalyst loading,1,2-methylene chloride as solvent, and1/2.3of molor ratio of phenyl acetylene with N-methyl pyrrole. Under the optimal conditions, isolated yield of1-methyl-3-(1-(1-methyl-1H-pyrrol-3-yl)-1-henylethyl)-1H-pyrrole was62%.