PIFA/TfOH-Mediated para -Selective C–H Triflation of Unprotected Anilines and Self-Coupling of Aryl Ethers

A metal-free PIFA/TfOH-mediated para-selective C–H triflation of unprotected aniline derivatives has been achieved. This protocol provides direct access to p-aryl triflates without the need for preinstalled directing or leaving groups. The reaction exhibits high para regioselectivity and is amenable to gram-scale preparation. The same activation manifold is further extended to aryl ethers for para-selective self-coupling.