Enantiopure Aromatic Saddles Bearing the Fenestrindane Core

The synthesis of enantiomerically pure, configurationally stable fenestrindane-based polyaromatic compounds with saddle-like structures is reported. Seven racemic fenestrane synthetic precursors were first screened by chiral HPLC for resolvability into enantiomers. Among the three resolvable precursors, a tribenzofenestrene derivative was resolved on a semipreparative scale, and the absolute configuration of the more slowly eluting enantiomer was established by X-ray crystallography. The enantiopure tribenzofenestrenes were then separately converted, in six steps, to the saddle-shaped fenestrindane derivatives in optically pure form. The two enantiomeric pairs of saddles were characterized by 1H and 13C NMR spectroscopy, mass spectrometry, and circular dichroism spectroscopy. All new compounds reported herein represent the first enantiopure non-natural carbocyclic fenestranes isolated to date.