Divergent Synthesis of Oxindole Derivatives via Cascade Deoxygenative Friedel–Crafts Cyclization of α ‐Ketoamides

3‐Substituted oxindoles are key motifs in natural products and pharmaceuticals. Previous syntheses required prefunctionalized substrates, transition‐metal catalysts, or strong acids under harsh conditions. Herein, we report a mild, metal‐free, and efficient alternative to the Barton–McCombie reduction for the synthesis of C‐3 functionalized oxindoles via deoxygenative intramolecular Friedel–Crafts alkylation of α ‐ketoamides employing Iodine and TMSOTf‐based activation modes in combination with a silane system. The process likely involves in situ silylium ion generation, regioselective cyclization, silane‐promoted deoxygenation, and rearomatization, yielding 3‐aryl/alkyl/halo/hydroxy‐oxindoles. This one‐step protocol is mild, scalable, and compatible with diverse functional groups.