Synthesis Of Ferrocene Hydrazone And Planar Chiral Ferrocene Indene

This research mainly carried out the synthesis of ferrocene hydrazone and planar chiral ferrocene indene,and studied their applications according to the structures and properties,which could divided into the following two parts.In the first part,in the synthesis of ferrocene hydrazone,the thesis first prepared a series of compounds derived from ferrocenone-derived hydrazone,and then proceeded the exploration tests to synthesize planar chiral ferrocene derivatives using ferrocene-derived hydrazone as the guide groups.The reaction of p-toluenesulfonyl hydrazide with different ferrocenones was used to synthesize ferrocenone-derived monohydrazone and ferrocenone-derived dihydrazone.Nuclear magnetic resonance(¹H NMR and ¹³C NMR),melting point and high-resolution mass spectrometry（HRMS）and other characterization methods were selected to characterize the synthesized of target products.After optimizing the reaction temperature and time,the yield is above 60%,and the more the number of substituents,the greater the steric hindrance,the higher the temperature and time requirements,and the yield is also affected to decreased,this law can provide guidance on the synthesis of ferrocene hydrazone compounds and the expansion of substrate.In the exploration of hydrazone as a guiding group,we hope to realize the efficient synthesis of planar chiral ferrocene derivatives through the construction of catalysts,bases,oxidants,and auxiliary systems to achieve C-H bond activation.We have tried four schemes,but the results are not ideal enough,and we failed to find a suitable system to prove that the hydrazone can function as a guiding group,but the construction of a planar chiral ferrocene derivative guided by a guiding group is of great significance and far-reaching impact in the field of organic synthesis,and it deserves our continuous attention and breakthroughs.In the second part,in the synthesis of planar chiral ferrocene indene,first we determined the acylation of ferrocene and its derivatives,zero-valent palladium catalyzed the asymmetric C-H bond arylation in the molecule,and the reaction route of reduction of sodium borohydride.At the same time,nuclear magnetic resonance(¹H NMR and ¹³C NMR),melting point,high resolution mass spectrometry（HRMS）,high performance liquid chromatography,single crystal diffraction and other characterization methods were used to characterize the synthesized target products.In the investigation of the effect of substituents on planar chiral ferrocene indene on planar chirality,the substitution of methoxy and chlorine at positions with small steric hindrance on the benzene ring resulted in higher ee value of 97.4%and 98.8%,respectively;Modifying cyclopentadiene under ferrocene,when the benzyl group is substituted,89.7%ee value is obtained.In the exploration experiment of forming a complex with metal titanium and zirconium,zirconium tetrachloride and titanium tetrachloride were subjected to an tentative reaction with ferrocene indene,but the expected product not be monitored.This scheme is still extremely attractive,the combination of planar chiral ferrocene indene with metal is what we expect as a polymerization catalyst and will continue to be explored in the future.The route is simple and easy to operate,the raw materials are cheap and easy to obtain,and the reaction conditions are mild,the obtained ferrocene indene compounds are widely used and have great research significance.