The synthesis of 8-aminoquinolines and 1, 10-phenanthrolines with substituents in α of the nitrogen has been performed through an inverse-demanding aza-Diels–Alder (Povarov reaction) in the fluoroalcohols TFE or HFIP. This path involves simple starting materials: 1, 2- phenylenediamines, enol ethers and aldehydes.