Abstract An unprecedented olefination reaction of secondary amines with carbon nucleophiles has been developed through C–N/C–H functionalization under metal-free oxidative conditions. In the presence of a stoichiometric amount of 2, 3-dichloro-5, 6-dicyano- 1, 4-benzoquinone (DDQ), a range of secondary N-alkylanilines smoothly underwent oxidative olefination with 2-alkylazaarenes, acetophenone, and malononitrile to give ...