Synthesis Of Carbon-carbon Bond And Carbon-nitrogen Bond Using Zirconocene Perfluorooctanesulfonate As A Catalyst

As the catalyst, Lewis acid plays an important role in organic synthesis. Organicmetal complexes developed quickly and Organic zirconium compounds as a Lewisacid, can catalytic many chemical reactions, and become chemical research hot spot.Since most zirconium compounds rapid decomposed in the condition of air and water,and the catalytic activity is not very high, thus limited their applications. The studyfound that the introduction of good electron-withdrawing groups enhanced the acidityof zirconium compounds and the stability of the water. In this work, our groupsynthesized a stable, resistant of water and oxygen, also has a strong acidicmetallocene perfluoroalkyl sulfonic acdi complexes: zirconocene bis(perfluorooctanesulfonate)s. Studies show that this compound could be a goodcatalyst to esterfication reaction, the eater exchange reaction, allyation reactions,Mannich reaction, etc. The catalyst can be reused, the experimental conditions aremild and easy to operate.In this article, the zirconocene bis (perfluorooctanesulfonate)s was used as thecatalyst for catalytic C-C bond, C-N bond formation. This strategy was succeeded inthe synthesis of the diindolylmethane derivatives, β-amino alcohols, amides, andamide alkyl naphthol derivatives. The specific works are as follows:1. Zirconocene bis (perfluorooctanesulfonate)s catalytic diindolylmethanederivatives synthesis. Under Room temperature conditions, with THF as the solvent,tha catalytic property of the indole with aldehydes/ketone reaction, synthesis of aseries of different structures diindolymethane derivatives. The whole experimentalprocedure can be achieved within short time and without strictly anhydrous anaerobicoperation. Besides, the catalyst can be reused, no by-products generated, and theproduction rate of more than90%.2. Zirconocene bis (perfluorooctanesulfonate)s catalytic β-amino alcoholsynthesis. Room temperature, solvent-free conditions, these complex catalysts of thesame amount of epoxy and amine addition to ring-opening reaction, and synthesis ofa series of different structures of β-amino alcohol, the production rate of more than80%, and the catalyst can be reused.3. Zirconocene bis (perfluorooctanesulfonate)s catalytic amides derivativessynthesis. The results show that: the solvent-free, heated to100℃, the complexescan effective catalysts molar amount of aliphatic carboxylic acid and amine amidation reaction occurs, and the catalyst can be repeatedly used, short reactiontime, no by-products generated and yield up to89%.4. Zirconocene bis (perfluorooctanesulfonate)s catalytic amide alkyl naphtholderivatives synthesis. THF as the solvent and heated to reflux, the complex canefficiently catalyze the molar amount of β-naphthol, acetamide and aldehyde/ketonereaction, the synthesis of the corresponding structure of the amide alky naphthol. Thecatalyst can be reused, the experimental procedure is simple, no by-productsgenerated, the production rate of more than87%.