Copper (II) acetate Intermolecular C (sp2)-H Amination of Directing Group with Electron-Rich Anilines

N-(naphthalen-1-yl) picolinamide are ubiquitously found in numerous biologically active naturalproducts, medicinally relevant scaffolds, pharmaceuticals, agrochemicals, dyes, and functionalizedmaterials [1]. Conventionally, they are synthesized through a palladium- or coppercatalyzedGoldberg cross-coupling between aryl halides and amines [2]. In recent years, metalcatalyzed C-H activation strategy provides a direct access to the functionalized amines obviatingthe need for aryl halides. In this vein, Pd, Ir, Rh catalysis have been explored with aminesand highly energetic azides. To circumvent the metal poisoning issues with amines, the use ofinexpensive first row transition metals such as manganese, iron, cobalt, nickel, and copper isemerging [3].Despite significant progress, copper-catalyzed/mediated C-H amination reactionswith electron-rich anilines remains an unsolved problem due to catalyst deactivation anddeleterious side reactions. Herein we report, a copper (II)-mediated C (sp2)-H amination ofbenzamides with electronically neutral or electron-rich anilines. A dramatic influence of Ditert-butyl peroxide (DTBP), was observed on the reaction outcome (Fig. 1). The present protocolalso demonstrates the synthesis of a number of non-steroidal anti-inflammatory drugs(NSAID’s).