Depending on the metal complexes employed, regiodivergent C–H direct chlorination on 8-acylaminoquinolines could be realized. While the stoichiometric CuCl2/base persistently gave the C5-monochlorination, the Pd(II)-catalyzed chlorination by using N-chlorosuccinimide (NCS) as a chlorine source led to variable results mainly relying on the substitution pattern of the 8-acylaminoquinolines and the loading of NCS. This work demonstrated not only an unprecedented access to divergently halogenated quinolines, but also a less studied C(sp2)–H functionalization mode, namely the single-electron transfer (SET) mediated C(sp2)–H functionalization.

Direct assembly of α-amino amides from N-alkyl amines and isocyanides through oxidative Ugi-type reactions in aqueous conditions, has been achieved in a Cu(I)–TBHP–surfactant catalysis system. Various N-alkyl amines and isocyanides could be tolerated in this reaction and furnish α-amino amides in moderate yields.

α-Amino imides can be accessed straightforwardly from tertiary amines through copper-catalyzed three-component reactions involving the direct functionalization of sp3 C−Hs adjacent to nitrogen atoms. This reaction has demonstrated a tolerance to a wide range of functionalizations and can be performed under very mild conditions. A plausible mechanism has been proposed in which an Ugi-type cascade assembly has been included.