Studies On The Synthesis And Characterization Of Chiral Ferrocenyl Amines

In this thesis, new methods were explored for synthesizing purely optical ferrocene derivatives. A series of chiral ferrocenyl amines with both center and planar chirality were obtained. The novel compounds6a-6e were characterized by1H NMR,13C NMR, HRMS, IR and Optical rotation. The main results obtained are as follows:1. The1,1’,2,2’-tetrasubstituted ferrocene derivative4a and1,1’,2,-trisubstituted ferrocene derivative4b were prepared via diastereoselective di-ortho-lithiation of (S,S)-3, which was derived from1,1’-ferrocenedicarboxaldehyde and (S)-2-(methoxymethyl)pyrrolidine.2. The synthesis methods of compounds5a and5b were developed from4a and4b by two methods.1) Direct oxidation with MnO2in12%and13%yields;2) Transformation from4a and4b to (S,S)-1,1’-bis(trimethysilyl)-2,2’-bis(acetyloxymet hyl)ferrocene and (S)-1-trimethylsilyl-2,2’-bis(acetyloxymethyl)ferrocene, then oxidation with MnO2in71%and72%yields. The former method is inferior to later one.3.6a and6b were obtained by the reaction of N-Boc-(S)-2-aminomethyl pyrrolidine and D-phenylglycinol with compound5a. And6c and6d were synthesized by the reaction of N-Boc-(S)-2-Aminomethyl pyrrolidine and D-phenylglycinol with trisubstituted ferrocenes5b. 4. Two methods were developed for the synthesis of1-trimethylsilyl-N-(substituted)-2-aza-[3]ferrocenophane:1) via direct lithiation of N-(substituted)-2-zza-[3]ferrocenophane VIII, then followed by treatment with trimethylsilylchloride;2) Condensation of N-Boc-(S)-2-aminomethyltetrahydropyrrole and (S)-1-trimethyl silyl-2,2’-bis(acetyloxymethyl)ferrocene.