Asymmetric Synthesis Catalyzed by Chiral Ferrocenylphosphine–Transition Metal Complexes. I. Preparation of Chiral Ferrocenylphosphines

• Published in: Bulletin of the Chemical Society of Japan Vol. 53; no. 4; pp. 1138 - 1151
• Main Authors: Hayashi, Tamio, Mise, Takaya, Fukushima, Motoo, Kagotani, Masahiro, Nagashima, Nobuo, Hamada, Yuji, Matsumoto, Akira, Kawakami, Sota, Konishi, Mitsuo, Yamamoto, Keiji, Kumada, Makoto
• Format: Journal Article
• Language: English
• Published: The Chemical Society of Japan 1980
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.53.1138

As chiral ligands for transition metal complex catalyzed asymmetric reactions, various kinds of chiral ferrocenylphosphines, which have planar chirality due to 1,2-unsymmetrically substituted ferrocene structure and also have a functional group on the side chain of the ferrocene nucleus, were prepared. (S)-N,N-dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine [(S)-(R)-PPFA], (S)-N,N-dimethyl-1-[(R)-1′,2-bis(diphenylphosphino)ferrocenyl]ethylamine [(S)-(R)-BPPFA], and their dimethylphosphino derivatives were prepared by way of lithiation of optically resolved N,N-dimethyl-1-ferrocenylethylamine. The 1-(dimethylamino)ethyl group on the ferrocenylphosphines was converted stereospecifically by nucleophilic substitution reactions into 1-methoxy-, 1-hydroxy-, 1-diphenylphosphino-, and several 1-(dialkylamino)ethyl groups. 1-Diphenylphosphino-2-(dimethylaminomethyl)ferrocene (FcPN) was optically resolved via its phosphine sulfide dibenzoyltartaric acid salt. The relationship between CD spectra of the chrial ferrocenylphosphines and the configuration of their planar chirality is discussed.