The Hydrogenation Reaction Of M₂and The Formation Of C-N Bond Using Zirconocene Perfluorooctanesulfonate As A Catalyst

Finasteride is a steroidal compound, which mainly used for the treatment ofbenign prostatic hyperplasia and Alopecia. Benign prostatic hyperplasia depends onthe conversion of testosterone to dihydrotestosterone within the prostate. Finasteridecan be very effective in reducing the content of dihydrotestosterone in the blood andprostate, to effectively improve the symptoms of benign prostatic hyperplasia and toincrease the speed of urine flow, it also can reduce prostate volume, and reduce the riskof treatment failure. methyl3-Oxo-4-aza-5α-androstene-17-carboxylate is a keyintermediate for Finasteride. In the study, effect of solvent, reaction temperature,inhibitors and the amount of catalyst on stereoselectivity in Pd/C-catalyzedhydrogenation of methyl3-Oxo-4-aza-5-androstene-17-carboxylate was explored. wefound the best selectivity was obtained by using20:10mixture of alcohols and acetic.On the basis of these experimental results, we opted the following ideal conditions forthis process:20:10methanol and acetic acid as ideal reaction medium,20%Pd/Cloading, temperature at60~70℃, pressure at1.5MPa and14~16h of stirring.Pd/C-catalyzed in the catalytic hydrogenation reaction is easy to inactivation, we alsoexamined the activation of Pd/C-catalyzed and found that Soxhlet extraction withtoluene on the catalyst allows deactivation of the catalytic activity has been greatlyimproved. Hydrogenation react with treated palladium carbon catalyst, and the yield is75%~85%.In recent years, with the development of transition metal organometalliccompound, organic reactions promoting by transition metal organometallic compoundaroused the universal concern of chemists, which has gradually become a researchfocus in the chemical field. A number of organic zirconium compounds serve as Lewisacid catalysts has been wide uded in Organic synthesis. however, some organiczirconium compounds chemically unstable due to water-sensitive and atmosphere–sensitive, and thus require harsh reaction conditions. the Lewis acid of some organiczirconium compounds is too mild to form carbon-carbon bond and carbon-nitrogenbond. The drawbacks Limit the broader application of the zirconium complexes.Therefore, it is of great significance to the synthesis of air stable and strong acidicorganic Zirconium complexes. One of the useful means for Enhance the acidity is toattach electron-withdrawing group(s) on zirconium. Perfluoroalkylsulfonate is such anelectron-withdrawing group and it’s reported perfluorooctanesulfonate metal compounds are air-stable and water-stable compound. In this paper, we synthesizeBiscyclopentadiene zirconium bisperfluorooctanesulfonate compound. its catalyticactivity is assessed in the organic synthesis. it is one of the hot spots of organicchemistry research. In the contents of the paper, we focus on forming carbon-nitrogenbond in the solvent-free conditions,1,5-Benzoheteroazepines was synthesisd withbiscyclopentadiene zirconium bisperfluorooctanesulfonate, and the yield is about90%.In addition, The catalytic activity of biscyclopentadiene zirconiumbisperfluorooctanesulfonate was assessed with aldehyde, ethyl acetoacetate andammonium acetate in Hantzsch reaction,the yield is about90%. The experimentalstudy found that the reaction has the advantages of mild reaction conditions, simpleoperation and high yield.