Synthesis Of Chiral Cyclohexanediamine-Triazole And Triazole-Au Complexe And Study On Application Of Triazole-Au Complexe In Three Component Reaction

In recent years, homogeneous gold catalysts have received more attention from scientists. Gold as catalyst has many unique advantages. Gold, as a soft Lewis acid, is easy to coordinate with soft base, which could activate alkyne containing of the triple bond as soft base. Therefore, the gold catalyst can complete some reactions which other catalysts are difficult to catalyze. However, there are many cationic gold catalysts for poor thermal stability. Due to its unique structure, triazole has strong coordination with gold and could be used as a ligand for heterogeneous gold catalyst to stabilize the gold, which in a certain extent breaks through the incompatible situation of gold catalysts activity and stability. In this paper, triazole cationic gold catalyst was applied in one pot three component reaction to synthesis 2,4 disubstituted quinoline compounds, so as to test the catalytic activity of triazole-gold catalyst in the reaction. Cyclohexanediamine as a class of important chiral diamine compounds in the past few decades has been widely used in asymmetric catalytic reactions, which chiral Salen- metal complexes as catalyst have achieved great success. In this paper we combined cyclohexanediamine with triazole compounds, synthesised a series of chiral diaminocyclohexane class triazole ligand, and plans to use this kind of ligands to catalyze asymmetric reaction. Innovative results are achieved as follows:(1) Triazole-gold catalyst was synthesised by 1H-Benzotriazole and Chloro(dimethyl sulfide)gold as raw material through three steps reactions with high yield. And for the first time the triazole-gold catalyst was used for the three component reaction of synthesis the quinoline derivatives. The catalytic results show that, compared to the simple cationic gold catalysts(Au Cl3, etc.) and cationic gold complexes which does not contain benzotriazole,the 1, 2, 3,-triazole-Au catalysts have better catalytic activity. Toluene as solvent and 110 0C reflux, 2, 4-disubstituted quinoline derivatives was synthesized by a series of aldehydes, aniline, alkyne as raw materials with 46-92% yield. The synthetic method broadened three triazole-gold catalyst application.(2) With ethyl chloroformate and phenylacetylene as starting material, a series of cyclohexanediamine triazole ligand were obtained by six steps reactions and the overall yield was 45%. This work provided the synthetic basis for the subsequent application of cyclohexanediamine triazole ligand.