Synthesis And Characterization Of Ferrocene Monosulfur,Disulfide Chiral Ligands

Ferrocene has good chiral ligand support.In recent years,the synthesis and application of ferrocene chiral sulfur ligands and ferrocene pyridine ligands have gradually attracted the attention of many scholars.This thesis carries out research from the following three directions:1.Synthesis and characterization of ferrocene aryl monosulfur chiral ligandsBased on the existing research results in the laboratory,using planar chiral ferrocene indene as the substrate,after lithium ion of n-butyl lithium and nucleophilic substitution of electrophilic reagent（aryl persulfide）,nine ferrocene aryl mono-sulfur ligands with planar and central chiral properties with electron-donating and electron-absorbing substituents and ortho,meso and para-substituents（4-Cl,4-Br,4-CF₃,2-CH₃,3-CH₃,4-CH₃,4-CH₂CH₃,4-C（CH₃）₃,4-OCH₃）were synthesized,with ee values of 97.9%-99%and de values of 92.4%-99.6%.This synthesis method is simple and easy to operate,and has good universality.The compounds were characterized by NMR(~1H NMR,¹³C NMR),high resolution mass spectrometry,high performance liquid chromatography and other characterization methods,and the ~1H NMR chemical shift of the hydrogen connected to the central carbon atom was analyzed.One crystal obtained was also analyzed by single crystal diffraction.It is found that a spatial configuration similar to regular tetrahedron is formed with the central chiral carbon as the center.2.Synthesis and characterization of ferrocene disulfide chiral ligandsSynthesis of disulfide ligands consisting of cyclohexyl sulfur and other sulfur:Seven chiral ferrocene disulfide ligands composed of cyclohexyl sulfur and other sulfur were obtained after relithium and electrophilic reagent（sulfide compound）attack,with ee value of 94.2%-99.1%and de value of 84.6%-99.3%.Synthesis of disulfide ligands composed of phenyl sulfur and other sulfur:In the same way as the synthesis of disulfide ligands composed of cyclohexyl sulfur and other sulfur,four ferrocene disulfide ligands composed of phenyl sulfur and other sulfur were obtained on the basis of ferrocene phenyl single sulfur ligands,with ee and de values up to99%.Under the same characterization method as above,through the analysis and comparison of the obtained six crystals and the comparative experiments,the reaction mechanism of the sulfur group and ferrocene single dentate sulfur ligand and the configuration composition of ferrocene chiral sulfur ligand were obtained.3.Synthesis and characterization of pyridyl ferrocene indene ligandsIn 3-bromide pyridine and ferrocene as reactants,formaldehyde in 2,2,6,6-tetramethyl piperidine basic magnesium chloride react under the action of lithium chloride compound,after the oxidation of manganese dioxide and palladium-catalyzed intramolecular ring closure reaction,the compound pyridyl ferrocene indene ketone,but its antipodal selectivity and application has not been further explored.