Journal of the American Chemical Society, Vol.139, No.5, 1806-1809, 2017
Streamlined Synthesis of Polycyclic Conjugated Hydrocarbons Containing Cyclobutadienoids via C-H Activated Annulation and Aromatization
The juxtaposition of fused cyclobutadienoid (CBD) with benzenoid creates intriguing alternating antiaromatic and aromatic conjugation. Synthetic accessibility of such molecules, however, has been challenging and limited in scope. We report a modular and streamlined synthetic strategy to access a large variety of polycyclic conjugated hydrocarbons with fused CBD. Synthesis was achieved through efficient palladium-catalyzed C-H activated annulation between abundant aryl bromides and oxanorbornenes, followed by aromatization under acidic conditions. The influence of four-membered ring was examined using spectroscopy, crystallography, and computation. This strategy will facilitate exploration on the chemical, structural, and electronic properties of such conjugated systems containing CBD.