Dual Palladium/Scandium Catalysis toward Rotationally Hindered C3‐Naphthylated Indoles from β‐Alkynyl Ketones and o ‐Alkynyl Anilines

Main observation and conclusion A new dual palladium/scandium catalysis starting from β‐alkynyl ketones and o ‐alkynyl anilines is reported for the first time, leading to the atom‐economic synthesis of rotationally hindered C3‐naphthylated indoles in moderate to good yields and high regioselectivity. This method can tolerate normal air conditions, and features the use of palladium/scandium cooperative catalysts without any ligand, facile double annulation involving various internal alkynes, and good functional group tolerance.