Synthesis, Structures, Resolution, and Chiroptical Properties of 1,16-Diaryl-Substituted Benzo[5]helicene Derivatives.

Abstract

An efficient route to the synthesis of benzo[5]helicene derivatives functionalized on the interior side of the helix was developed, and resulted in a series of 1,16-diaryl-substituted benzo[5]helicene derivatives starting from easily available 7-methoxytetralone. X-ray crystal structures showed that the benzo[5]helicene derivatives had highly helical, twisted structures, and could all create hierarchical packing architectures with alternating P and M layers in the solid state. Moreover, seven pairs of enantiomers based on 1,16-diaryl-substituted benzo[5]helicene derivatives were also obtained by efficient resolution through HPLC with semipreparative chiral columns. The enantiomers all showed clear mirror-image circular dichroism (CD) spectra and high specific optical rotations, and their absolute configurations were determined by X-ray crystallography. Interestingly, a helical nanotubular structure was formed by the self-assembly of one enantiomer through halogen bonding. Furthermore, the enantiomers were found to have high racemization barriers and thermostability, which might be caused by the introduction of aryl substituents at the C1(C16) position.