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
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