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As a result of detailed mechanistic and kinetic studies, we have proposed that PdX2‐catalyzed oxidative coupling of o‐alkynylanilines 1 with terminal alkynes 2 under aerobic conditions is initiated by aminopalladation of 1 followed by ligand exchange of the resulting σ‐indolylpalladium(II) complex with 2, reductive elimination and N‐demethylation. Side reactions associated with intermediates on the...
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