A Study On Tertiary Amines Catalyzed Aza-Michael Additions

Since the ground-breaking work of Barbas, List, Jacobsen, J?rgensen, MacMillan and many other researchers in the early 2000s, the field of organocatalysis has attracted more and more attention and participation."The golden age of organocatalysis"has already dawned. Under the breathtaking pace of growth in the field of organocatalysis since 2000, a day hardly passes without a new organocatalytic reaction emerging in the electronic journals. However, only one article with regard to asymmetric organocatalytic intermolecular aza-Michael addition had been reported by the end of 2005, both opportunities and challenges triggered us to carry out the work in this thesis.To develope a reaction system of asymmetric organocatalytic aza-Michael addition catalyzed by tertiary amines, some preliminary investigation was conducted. Firstly, three types of N-nucleophiles including hydrazine derivatives, sulfonamides and imides were designed and prepared. After the evaluation in the model reaction of conjugate addition ofβ-nirtostyrene catalyzed by quinine, 4-nitrophthalimide was screened out as the most efficient N-nucleophile.The organocatalytic aza-Michael addition of 4-nitrophthalimide to nitroolefins was systematically studied in the second part of this work, and the effects of catalyst, solvent, temperature and reaction time were evaluated successively. A high yield up to 93% and a moderate enatioselectivity of 11% e.e. were gained under the optimized reaction conditions.Finally, we examined the scope of Michael acceptors of 4-nitrophthalimide. The activities of conjugate addition of 4-nitrophthalimide to a series of Michael acceptor such asα,β-unsaturated aldehydes, ketones, carboxylic esters and amides were investigated. A parallel experiment using phthalimide as the N-nucleophile was also conducted.