Unbiased C3‐Electrophilic Indoles: Triflic Acid Mediated C3‐Regioselective Hydroarylation of N−H Indoles

The direct dearomative addition of arenes to the C3 position of unprotected indoles is reported under operationally simple conditions, using triflic acid at room temperature. The present regioselective hydroarylation is a straightforward manner to generate an electrophilic indole at the C3 position from unbiased indoles in sharp contrast to previous strategies. This atom‐economical method delivers biologically relevant 3‐arylindolines and 3,3‐spiroindolines in high yields and regioselectivities from both intra‐ and intermolecular processes. DFT computations suggest the stabilization of cationic or dicationic intermediates with H‐bonded (TfOH)( n ) clusters.