Synthesis and Properties of Twisted and Helical Azulene Oligomers and Azulene-Based Polycyclic Hydrocarbons.

The construction of 1,2-position-connected azulene oligomers was achieved. In the crystal packing structure of the terazulene, two molecules of (R )- and (S )-configurations formed a pair. Variable temperature NMR measurements and theoretical calculations of the quaterazulene suggest that the helical and syn-type structure with terminal azulene overlap is more stable. Two kinds of fused terazulenes (1,2''-closed and 1,8''-closed) were also synthesized by intramolecular Pd-catalyzed C-H/C-Br arylation of the terazulene moieties. X-ray structure analysis of 1,2''-closed terazulene revealed a planar structure, while an analysis of 1,8''-closed terazulene performed on a C co-crystal revealed a curved structure forming a 1 : 1 complex covering the co-crystal. Nucleus-independent chemical shift (NICS) calculations carried out for the central seven-membered ring of 1,8''-closed terazulene showed a positive value, suggesting anti-aromatic properties.