We report the efficient synthesis of cycloalkyl-fused naphthalenes through the [4 + 2]-cycloaddtion/decarboxylative aromatization of alkyne-tethered aryne insertion adducts. These scaffolds were difficult to synthesize using conventional reactions. The reaction proceeds via the formation of a benzopyrylium intermediate followed by intramolecular [4 + 2] cycloaddition and a subsequent decarboxylation pathway. This method is also compatible with allene-tethered substrates to afford similar products. In addition, the one-pot synthesis of polysubstituted naphthalenes via aryne insertion/benzannulation has also been developed in good yield.

Cascade aza-Piancatelli reaction and [3 + 3]/[4 + 2] cycloaddition reactions are carried out using the ideality principles of pot, atom, and step economy (PASE) synthesis. The reaction resulted in generation of octahydro-4H-cyclopenta[b]pyridin-6-one scaf-folds. Moreover, octahydro-5,7a-epoxycyclopenta [cd]isoindol-4one frameworks of gracilamine alkaloid and a novel decahydro-1H-dicyclopenta [cd,hi]isoindol-6-one were also realized in good yields with excellent regio-and diastereo-selectivities.

Aryne insertion reaction with 2-aroyl malonates/ cyanoesters lead to the formation of diarylmethane or chromones depending on the substitution on the aryne ring. Presence of electronegative atom at ortho position...