Condition-Controlled Selective Synthesis of Pyranone-Tethered Indazoles or Carbazoles through the Cascade Reactions of N-Nitrosoanilines with Iodonium Ylides

Presented herein is a condition-controlled selective synthesis of pyranone-tethered indazoles or carbazole derivatives via the cascade reactions of N-nitrosoanilines with iodonium ylides. Mechanistically, the formation of the former involves an unprecedented cascade process including nitroso group-directed C(sp2)–H bond alkylation of N-nitrosoaniline with iodonium ylide followed by intramolecular C-nucleophilic addition to the nitroso moiety, solvent-assisted cyclohexanedione ring opening, and intramolecular transesterification/annulation. On the contrary, the formation of the latter involves the initial alkylation followed by intramolecular annulation and denitrosation. These developed protocols feature easily controllable selectivity, mild reaction conditions, a clean and sustainable oxidant (air), and valuable products that are structurally diverse. In addition, the utility of the products was showcased by their facile and diverse transformations into synthetically and biologically interesting compounds.