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Mechanistic Insights into CN Coupling Catalyzed by 1,3‐Diketonate‐Ligated Copper: Unprecedented Activation of Aryl Iodide

Mechanistic studies on dative N,N-ligands have established that the active catalyst is a [LCuNu] species (Nu = amidate, imidate) in equilibrium with unreactive [CuNu2] . [LCuNu] complexes have however never been generated nor detected in the context of real catalytic reactions. The mechanism of their reaction with aryl halides is still under debate, taking the form of a) oxidative addition to give [ArCuX(Nu)L] , which has never been experimentally established but is supported by DFT calculations, or b) inner-sphere electron transfer with formation of intermediate [LCu + Nu ArX ] . A mechanism involving an outer-sphere electron transfer (SET) has been ruled out on the basis of lack of correlation between reactivity and reduction potentials of ArX. In contrast to dative N,N-ligands, no mechanism of reactions involving anionic 1,3-diketonate ligands has been established based on experiments. Recent DFT calculations proposed a SET mechanism. In this context, we report herein a mechanistic study, based on experiments and DFT calculations, on N-arylations of ArI, catalyzed by copper(I) associated to a 1,3-diketonate. Notably, DFT calculations revealed an unprecedented activation of ArI. Catalytic C N cross-coupling reactions were first performed between aryl iodides and N-cyclohexylamine, CyNH2 (1) in the presence of a base (Cs2CO3) in DMF. The CuI catalyst was associated with a 1,3-diketone preligand (LH, Table 1). Our purpose was not to optimize the catalytic reactions but to