Light-Induced Generation and Cycloaddition Reactions of Benzyne: Synthesis of Naphthoxindoles E and Annulated Indolizines

By virtue of their high electrophilic nature, benzynes serve as reactive dienophiles in numerous cycloaddition reactions. However, in situ generation of benzyne involves either base-mediated thermal reactions, low-temperature conditions, or metal-catalyzed reactions of substituted arenes. This limits the applicability of benzynes as suitable dipolarophiles in cycloaddition reactions. Herein, we have reported a UVA (365 nM)-induced in situ generation of benzynes (from triazenyl benzoic acid) and subsequently their 4 + 2 Diels–Alder and 3 + 2 cycloaddition reactions with appropriate reaction partners such as N-protected alkylidene oxindole carboxylates and pyridinium ylides to afford naphthoxindoles E and pyrido2,1-aisoindole, respectively, in moderate to excellent yield. The reactions occurred at room temperature and under reagent-free reaction conditions. Each of these building blocks is pharmaceutically relevant; hence, this highlights an interesting strategy to access these classes of compounds.