Regiospecific 2,3‐Dialkylindole Synthesis Enabled by Alkylpalladium 1,2‐Migration to In Situ Formed Aldimine

2,3-Dialkylindoles play crucial roles in natural products and pharmaceuticals, but the step-efficient and regioselective construction of such privileged structures remains a long-standing challenge. Here, we report a regiospecific non-Fischer indole synthesis through chemoselective 1,2-migratory addition of alkylpalladium to an aldimine intermediate, formed in situ through a palladium hydride-triggered sequential isocyanide and intramolecular olefin insertion. This unprecedented 1,2-migratory addition leads to formal C═C bond cleavage and isocyano carbon insertion between the two sp² carbons, offering a novel approach to specific 2,3-dialkyl substituted N─H free indoles from readily available alkyl substituted 1-isocyano-2-vinylbenzenes.