Gold‐Catalyzed Regioselective Tetradehydro‐Diels‐Alder Reaction of Yne‐Ynamides: Access to 2,3‐Dihydrobenzo[f]indoles

Abstract Presented herein is a gold(I) catalyzed intramolecular tetradehydro‐Diels‐Alder (TDDA) reaction of alkyne‐tethered‐ynamides for the construction of structurally complex 2,3‐dihydrobenzo[ f ]indole derivatives. The mechanism of the regioselective benzannulation reaction was rationalized by means of density functional theory (DFT) calculations. Substrates having an aryl group at the ynamide terminus are exclusively participating in this TDDA reaction under gold catalysis.