Synthesis of Indoloquinolinone Derivatives via Organoiodine‐Catalyzed Highly Chemoselective C−H Amidation

New catalytic approaches for the synthesis of indoloquinolinone derivatives have gained significant interest, as indoles are pivotal structural elements in biologically active molecules and natural products. Despite the availability of well‐established transition‐metal catalytic methods for constructing such important frameworks, the organocatalytic synthesis of indole‐based substrates is still underdeveloped and remains a formidable challenge. In this context, we have developed a highly chemoselective C−H amidation reaction catalyzed by organoiodine without dearomatization of indole‐fused reactants in a complex oxidative system. Notably, the introduction of a nitro group at the C5‐position of indole substantially enhances the reactivity of the substrates, thereby effectively accelerating the oxidative reaction under catalytic conditions. This highly selective transformation of diphenylindoles into indoloquinolinones offers a promising strategy for synthesizing diverse and bioactive indole alkaloids.