Synthesis And Characterization Of Ferrocenyl Monodentate And Bidentate Sulfur/Phosphine Ligands

Featuring in adequate rigidity,easily derivatization and so many other desirable advantages,chiral ferrocenyl ligands have been implemented in asymmetric catalysis widespreadly.One well-known example is Josiphos type ligands,there have been a large amount of reports about application of Josiphos in asymmetric hydrogenation,asymmetric arylation,asymmetric hydroamination and so forth.Ferrocenyl P,S-ligands,however,still remained scarcely explored and synthesized to our knowledge.In this thesis,several researches we have conducted are as follows.(1)Ferrocene indene and its derivatives were synthesized utilizing two methodologies.The ferrocenylindene carbanion was furnished through deprotonation of ferrocene indenes using n Bu Li as strong base.The nucleophilic substitution proceeded between the carbanion and disulfide electrophiles to yield 8 ferrocenyl monodentate sulfur ligands.The structures of these 8 ligands were characterized by HRMS,NMR and other methods.The ee values are 29%—98.7% and de values are89%—99.6% examined by HPLC.(2)Changing the electrophiles to chlorophosphines,9 ferrocenyl monodentate phosphine ligands were synthesized and characterized by HRMS,NMR and other methods.The results of HPLC showed that the ee values are 95.5%—99.7% and the de values are 59.8%—99.4%.The absolute configuration,bond lengths and angles of phosphine ligand was demonstrated by X-ray single crystal diffraction.(3)With the monodentate sulfur ligands in our hand,the active remaining hydrogen in the methylene position can be deprotonated once more and generate carbon anion again.By doing so,we prepared several bidentate ferrocene ligands containing sulfur and phosphorus atoms.