Novel Chiral Ferrocene Ligand Design, Synthesis, And Nature Study

Owing to wider applications, the synthesis of chiral compounds is becoming an important hotspot in the chemical synthesis field. Chiral compounds are mainly synthesized by asymmetric catalysis using chiral catalyzer, which have advantages such as mildness reaction conditions, good diastereo-selectivity, and convenient obtainment of the potential chiral compounds. The fact that chiral source of chiral catalyzer comes from chiral ligands makes that chiral ligands are keys in synthesis of single isomer.In recent 30 years, thousands of chiral ligands were widely applied in lots of asymmetric catalysis reactions and quite good outcomes were obtained. Among numerous chiral ligands, the ligands with ferrocene acting as framework, especially 1, 2-disubstituted planar chiral ferrocene, become a kind of the most widely studied ligands for their unique traits.In this work, optically pure N, N-Dimethyl-1-ferrocenylethylamine was first prepared by raw material-ferrocene through Vilsmeier reaction, nucleophilic addition with Grignard reagent, esterification, aminolysis reaction and resolution. Then, (R, Sp)-N, N-Dimethy-l-(2-formlyferrocene)ethylamine and (S, Rp)-N, N-Dimethy-1-(2-formlyferrocene)ethylamine were synthesized by the orthodirecting effect of N, N-Dimethyl on the ferrocene. Next, the active aldehyde was modified and a series of new diamine ferrocenyl chiral ligands and other new ferrocenyl chiral ligands were synthesized. Two of these new ligands were characterized by X-ray single crystal diffraction analysis.Finally, referenced to literature, some original work has been performed:1. An appropriate synthesis route of N, N-Dimethyl-1-ferrocenylethylamine was designed with ferrocene as raw material.2. New chiral ferrocene ligands containing two nitrogensⅡ-Ⅵwere synthesized. This reaction consists the processes of condensation and deoxidization. These kinds of compounds are potential bidentate chelate ligands due to good coordination ability of nitrogen atoms. 3. Novel meta-stable salicyloyl hydrazideⅦ,Ⅷwere synthesized.4. New kinds ofα,β-unsaturated ketonesⅨ-Ⅺwere synthesized by aldolcondensation. These kinds of ligands own planar chirality and central chirality.