The Synthesis of Optically Active Primary Amino[3]ferrocenophanes

Abstract

Treatment of 1,1′-diacetylferrocene (1) with dimethyl­amine and TiCl₄ yielded the unsaturated dimethylamino-substituted [3]ferrocenophane product 2. Its catalytic hydrogenation gave the corresponding saturated [3]ferrocenophane system 3 (trans-cis 7:1). Quaternization of 3 followed by amine exchange using (R)- or (S)-1-phenylethylamine (8), respectively, proceeded with overall retention. Chromatographic separation gave the pure diastereoisomers (6S,9S,15R)-9 and (6R,9R,15R)-9 each in ca. 30% yield. Subsequently the benzylic (1-phenylethyl) auxiliary was removed from nitrogen by catalytic hydrogenolysis using ammonium formate as hydrogen donor to yield the enantiomerically pure primary [3]ferrocenophane amines (6S,9S)-10 and (6R,9R)-10, respectively. Complexes (6R,9R,15S)-9, (6S,9S,15R)-9, and (6R,9R)-10 were characterized by X-ray diffraction.

Key words

ferrocenophanes - amines - stereoselectivity - debenzylations - chiral auxiliaries

References

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10

Crystal structure analyses: data sets were collected with a Nonius KappaCCD diffractometer, equipped with a rotating anode generator Nonius FR591. Programs used: data collection COLLECT (Nonius B.V., 1998), data reduction Denzo-SMN (Otwinowski, Z., Minor W. Methods in Enzymology, 1997, 276, 307), absorption correction SORTAV (Blessing R. H. Acta Crystallogr. 1995, A51, 33; Blessing R. H. J. Appl. Crystallogr. 1997, 30, 421), structure solution SHELXS-97 (Sheldrick G.M. Acta Crystallogr. 1990, A46, 467), structure refinement SHELXL-97 (Sheldrick G. M. Universität Göttingen, 1997), graphics SCHAKAL (Keller E. Universität Freiburg, 1997). Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-233801-233803. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: [phone], e-mail: [e-mail]].