Unusually Short H···H Contacts in Intramolecularly Cyclized Helically Fused Anthracenes

Hiroki Fukuda, Eiji Tsurumaki, Kan Wakamatsu, Shinji Toyota

The intramol. coupling of dichloro-substituted helically fused anthracenes using the Yamamoto coupling yielded cyclized products with sterically congested mol. structures. The X-ray anal. and DFT calculations showed that the aromatic framework adopted a nonplanar structure with a twisted conformation about the newly formed single bond, which acts as a chiral axis. Interes tingly, the X-ray structure obtained through the Hirshfeld atom refinement revealed short interat. distances between the inner hydrogen atoms (1.648-1.692 Å), much shorter than the sum of their van der Waals radii. Owing to these unusually short contacts, the 1H NM R spectrum exhibited a signif icant deshielding (12.5 ppm) and a large nuclear Overhauser effect (44%) . Addnl., the IR spectrum displayed a high-frequency shift of the C-H stretching vibration. These observations, along with the noncovalent interaction plot indicative of a characteristic steric environment, strongly support the presence of steric hindrance. Moreover, dynamic N MR measur ement of the mesityl-substituted derivative yielded a barrier to helical inversion of 84 k J mol-1. The optical properties and crystal packing of the cyclized products are also reported.

Chem. Eur. J.

30

41

e202401627

10.1002/chem.202401627