An approach to helical tubular self-aggregation using C-2-symmetric self-complementary hydrogen-bonding cavity molecules

In an approach to helical self-aggregation, C 2 -symmetric cavity compounds based on the fusion of the bicyclo[3.3.1]nonane and indole framework and incorporating two 2-pyridone hydrogen-bonding motifs, compounds (-)-4 (pyrrole N-butyl) and (-)-5 (pyrrole N-decyl), have been synthesized. The 2-pyridone AD-DA hydrogen-bonding motif failed to operate in the solid state as demonstrated by X-ray diffraction analysis of (-)-4. Instead, the hydrogen-bonded (D-A) chains ⋯O=C-N-H⋯O=C-N-H⋯O=C-N- H⋯, interconnecting columnar stacks, comprise helices of the right-handed (P) chirality motif. In solution, the aggregation of (-)-5 was studied by NMR, electronic, and CD spectroscopies, and VPO measurements. These investigations strongly suggest that (-)-5 associates to oligomers in CHCl 3 and CH 2 Cl 2 using the 2-pyridone motif, fitting the equal K model, and that π-stacking can be ruled out as a mode of aggregation. We conclude that the so formed aggregates of (-)-5 have a helical structure, based on the fact that only helical tubular structures can result when enantiomerically pure 5 uses its 2-pyridone AD-DA hydrogen-bonding motifs for aggregation. \ua9 2006 American Chemical Society