Aminopalladation‐Triggered Carbene Insertion Reaction: Synthesis of 2‐(1H‐Indol‐3‐yl)acetates

Abstract The first example of a nucleopalladation‐triggered carbene insertion reaction for the synthesis of C‐3 alkylated indole derivatives from ortho ‐alkynyltrifluoroacetanilides and α‐diazoacetates is presented; it involves a palladium catalyst and a weak base in the open air. Yields range from 49–88% with excellent functional group tolerance. The reaction proceeds through intramolecular aminopalladation of alkynes followed by carbene insertion. Migratory insertion of the carbene into the σ‐indolylpalladium intermediate was favored over NH insertion. magnified image