Cyclic Alkyne Approach to Heteroatom-Containing Polycyclic Aromatic Hydrocarbon Scaffolds

Abstract

We report amodular synthetic strategy for accessing heteroatom-containing polycyclic aromatic hydrocarbons (PAHs). Our approach relies on the controlled generation of transient heterocyclic alkynes and arynes.T he strained intermediates undergo in situ trapping with readily accessible oxadiazinones.F our sequential pericyclic reactions occur, namely two Diels-Alder/retro-Diels-Alder sequences,w hich can be performed in astepwise or one-pot fashion to assemble four new carbon-carbon (CÀC) bonds.T hese studies underscore howthe use of heterocyclic strained intermediates can be harnessed for the preparation of new organic materials.

Modular Synthesis of Unsymmetrical Doubly-ring-fused Benzene Derivatives Based on a Sequential Ring Construction Strategy Using Oxadiazinones as a Platform Molecule

“…In summary, we have developed an efficient two-step benzene ring construction method using oxadiazinones as a platform molecule. 26,27 Sequential reactions of oxadiazinones with cycloalkynes and arynes enabled preparation of partially reduced polyaromatics in a modular synthetic manner. Since the synthesis of partially reduced polyaromatics by selective reduction or oxidation is not easy, our method would be beneficial for preparing such compounds useful in materials chemistry and pharmaceutical science.…”