Studies On Air-promoted Metal-catalyed Aerobic N-alkylation Reaction Of Amines With Alcohols

More and more attentions have been focused on the synthesis ofnitrogen-containing compounds for its wide existence in various naturalmedicines and important chemicals, pharmaceutical intermediates.Compared to the other methods of constructing C-N bond such asBuchwald-Hartwig amination, reductive amination of carbonylcompounds and amines, and hydroamination of carbon-carbonunsaturated compounds, the N-alkylation reactions of amines andalcohols have many advantages, therefore, this method has attract moreattention. Most of these catalytic systems are based on the noble metalcatalysts such as Ru and Ir.Although Ru, Rh, Ir have many similar properties, the use of Rh inthe N-alkylated reactions of amines and alcohols has rarely been reported.Based on our previous work, a new type of air（O₂）-promoted N-alkylationcatalytic system based on Rh will be put forward in this thesis.Air promoted N-alkylation reactions of amines and alcohols catalyzedby transition metals were studied first. In this part, the role of O₂inRhCl（PPh₃）₃-K₂CO₃-O₂catalytic system was investigated, then theinfluence of air to the reaction was investigated when it was catalyzed byother metal catalysts such as Ru, Rh, Ir. Also the applicability of this kindof M （Ru, Rh, Ir）-Base-O₂catalyst system was examed.Secondly, the catalytic properties of MnO₂-K₂CO₃-O₂to N-alkylationreactions of sulfonamides/heteroaromatic amines/arylamines withalcohols were investigated. This catalytic system not only makes full useof O₂in the air, but also avoids the use of noble transition metals, whichmakes this method more environment friendly and economical.