New reactivity of 6,6-bis-donor-substituted pentafulvenes: one-step synthesis of highly substituted [3]cumulene and dihydropentalene

We report the preparation of a 6,6-bis[(4-N,N-dimethylanilino)ethynyl]pentafulvene from a 6,6-dibromopentafulvene and 4-ethynyl-N,N-dimethylaniline under Sonogashira cross-coupling conditions. A push–pull [3]cumulene was formed unexpectedly during this reaction in moderate yield. The 6,6-bis[(4-N,N-dimethylanilino)ethynyl]pentafulvene was reacted with tetracyanoethylene, and an unprecedented 1,2-dihydropentalene was obtained in high yield as the exclusive product. The structures of the new compounds are supported by X-ray analysis, and a reasonable mechanism for their formation is proposed. We also report their interesting opto-electronic properties, as studied by UV/vis spectroscopy and cyclic voltammetry (CV).

A 6,6-bis[(4-N,N-dimethylanilino)ethynyl]pentafulvene has been prepared using a 6,6-dibromopentafulvene and 4-ethynyl-N,N-dimethylaniline under Sonogashira cross-coupling conditions. A push–pull [3]cumulene was formed unexpectedly during this reaction in moderate yield. The 6,6-bis[(4-N,N-dimethylanilino)ethynyl]pentafulvene was reacted with tetracyanoethylene, and an unprecedented 1,2-dihydropentalene was obtained in high yield as the exclusive product.Figure optionsDownload as PowerPoint slide