Study On Copper-catalyzed Reactions Of Oximes And Their Derivatives

Oximes and their derivatives are valuable synthetic building blocks. They has been applied in various of organic transformations in the last dacade. Recently, transition metal-catalyzed organic synthesis methods are also achieved many developments. Among metal-catalyzed reactions (such as iron、palladium、rhodium、copper et al.), the copper catalyst plays an important role due to its low-cost and low toxicity. Therefore, the development of efficient copper-catalyzed reaction of oximes has great significance.Firstly, the copper-catalyzed direct synthesis of Z-iodoenamides from ketoximes was developed in this thesis. The reaction allows gram-scale synthesis of iodo-enamide products. The detailed reaction mechanism was investigatived:firstly, the oxime acetate is obtrained by acylation of oximes. Next, oxime acetate reacts with Cu+ to afford enamide and Cu2+ by two-step single electron transfer reaction. Subsequently, the iodoenamides were got via oxidation and iodination of enamides in the catalyzing of Cu2+. Moreover, the Z-iodo-enamide products have been applied to synthesize substituted oxazoles, dienes, β-phenoxyl enamides, eneynes,β-acyl-enamides and pyrroles. Then, this thesis combines a concept of green chemistry, which combined reductive acylation of oximes and oxidative coupling of terminal alkynes without terminal oxidants and terminal reductants. It is achieved green organic synthesis of enamides and 1,3-diynes. The reaction time is significantly shortened comparing with the previously reported about the synthesis methods of enamides. Morever, a variety of special structure enamides were easily synthesized.