Hypervalent Iodine Reagent‐Promoted Alkoxylation of Indole Derivatives: Synthesis of 3,3‐Disubstituted Oxindoles

A catalyst‐free intermolecular dearomatization reaction of indoles with hypervalent‐iodine‐based nitrooxylating reagent is reported. Various alkoxyated 3,3‐disubstituted oxindoles bearing a quaternary carbon stereogenic center are obtained in good to excellent yields (up to 92%) under mild conditions. Meanwhile, the obtained products can undergo a variety of transformations smoothly, including Sonogashira coupling reaction, Suzuki coupling reaction, and demethylation reaction mediated by BBr 3 . In addition, natural product (±)‐convolutamydine A is synthesized by employing this method as the key step, showcasing the synthetic potential of the current method.