Formation Of Carbon-nitrogen(phosphorus) Catalyzed By Biscyclopentadienezirconium Bisperfluorooctanesulfonate

Organometallic Lewis acid as a catalyst has been widely used in organic synthesis.But, the organometallic Lewis acid catalyst mainly exists several problems (1) poorstability, air-or moisture sensitive (2) lower catalytic activity, can’t achieve the desiredresult.(3) high toxic, catalytic system is not environmental-friendly.(4) expensive,hard to use in industrialize produce. Therefore, how to design and synthesis of a stable,catalytic efficient, cheaper, environmental-friendly organometallic Lewis acid is keyissue for any scientists.In recent years, Research on organic zirconium metal complexes as Lewis acid isparticularly active for scientists, Some of them has widely used in organic synthesis.Such as: Zirconocene Dichloride and its derivatives, trifluoromethyl sulfoniczirconium complexes. But they are very sensitive to air and water and easily absorbentdeliquescence. Also the reaction requires relatively harsh conditions. Some ofzirconium complexes acidity are lower, it is difficult to effectively promote theformation of carbon-carbon bonds, carbon-heteroatiom bonds. Hence, It is especiallyimportant to synthesize a serial of air-stable, water-tolerant and high catalytic efficientcatalyst in organometallic Lewis acid catalysis chemistry.According to reports in the literature, long chain Perfluorooctanesulfonates metalcomplexes are very stable to air and moisture, and perfluorooctane sulfonic group withstrong electron-withdrawing capability can effectively strengthen the acidity ofmetallocene complexes. Our group synthesized hydrophobic and air-stableBiscyclopentadiene zirconium bisperfluorooctanesulfonate Lewis catalyst. Moreover,It has been successfully applied to build the carbon-carbon bond formation. Such as:Friedel-Crafts reaction, Mukaiyama-aldol reaction, allylation of aldehydes, Mannichreaction, glycosylation reaction and so on. Catalytic system showed reusability.Therefore, The paper use the high catalytic activity of Biscyclopentadienezirconium bisperfluorooctanesulfonate as a catalyst and build carbon-heteroatiombonds formation, The contents of the paper include three parts:(1) I studied the reaction of DEP with aromatic aldehydes or ketone and aromaticamines and synthetized α-Amino phosphonates at room temperature, solvent-free, andyield of90%or more. The catalyst show high reusability.(2) I studied the reaction of aldehydes,1,3-dicarbonyl compound and urea andsynthesied a series of3,4-dihydropyrimidin-2(1H)-ones. Reaction temperature at 100℃, solvent-free, yield of92%or more.The reaction condition is mild and easy tooperate. The catalyst show high reusability.(3) I studied the reaction of aldehydes with o-phenylenediamine and synthetizedbenzimidazole and its derivatives. At room temperature, solvent-free, The reaction ofdifferent molar ratio of aldehydes with o-phenylenediamine generate different products,The experimental results demonstrate a certain selectivity.