Highly Distorted Multiple Helicenes: Syntheses, Structural Analyses, and Properties

A series of hexapole helicenes (HHs) and nonuple helicenes (NHs) were prepared from 1,3,5-tris[2-(arylethynyl)-phenyl]benzene through two steps, namely, iodocyclization and subsequent palladium-catalyzed annulation with ortho-bromoaryl carboxylic acids. The crucial advantages of this synthetic method are the facile introduction of substituents, high regioselectivity, and efficient backbone extension. Three-dimensional structures of three C1-symmetric HHs and one C3-symmetric NH were elucidated using X-ray crystallography. Unlike most conventional multiple helicenes, the HHs and NHs investigated herein possess a unique structural feature where some double helical moieties share a terminal naphthalene unit. Chiral resolution of a HH and an NH was successfully achieved, and the enantiomerization barrier (Delta H double dagger) of the HH was experimentally determined to be 31.2 kcal/mol. A straightforward method for predicting the most stable diastereomer was developed based on density functional theory calculations and structural considerations. It was found that the relative potential energies (Delta Hrs) of all diastereomers for two HHs and one NH can be obtained using minimal computational effort to analyze the types, helical configurations, numbers, and Delta H(MP-MM)s [= H(M,P/P,M) - H(M,M/P,P)] of the double helicenyl fragments.

Automated summary

A series of hexapole helicenes (HHs) and nonuple helicenes (NHs) were synthesized from 1,3,5-tris[2-(arylethynyl)-phenyl]benzene through iodocyclization and palladium-catalyzed annulation. These helicenes exhibited unique structural features and were resolved into their enantiomers. The relative potential energies of their diastereomers were predicted using density functional theory calculations and structural considerations.