Base-Mediated Annulation of Electrophilic Benzothiophene with Naphthols and Phenols: Accessing Benzothiophene-Fused Heteroacenes.

A base-mediated annulation of 2-nitrobenzothiophenes with naphthols was realized for the synthesis of hitherto unknown class of heteroacenes, namely benzothieno[2,3- b ]naphthofurans. By using naphthols with a hydroxyl group positioned at 1st or 2nd position, we could synthesize two positional isomers, benzothieno[2,3- b ]naphtho[2,1- d ]furans or benzothieno[2,3- b ]naphtho[2,3- d ]furans. The annulation was found to be general with a range of substituted 2-nitrobenzothiophenes and naphthols. This heteroannulation of benzothiophene was extended using a range of phenols affording the corresponding benzothieno[2,3- b ]benzofurans in moderate yields. The basic photophysical properties of these heteroacenes were evaluated, and we also demonstrated the applicability of this annulation on the gram scale.