A time-efficient, integrated and continuous-flow platform has been developed for real-time, high-throughput studies on phthalide and API synthesis from ketone–O2 reactions.

Benzyne insertion to build the privileged scaffold of a [6.8.6]-tricyclic framework on polycyclic and sp 3 -rich natural products has been developed. The formation of the [6.8.6]-tricyclic ring system is solvent dependent.

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.