Aromatic Cyanoalkylation through Double C–H Activation Mediated by Ni(III)

Herein we report an atom- and step-economic aromatic cyanoalkylation reaction that employs nitriles as building blocks and proceeds through Csp2–H and Csp3–H bond activation steps mediated by NiIII. In addition to cyanomethylation with MeCN, regioselective α-cyanoalkylation was observed with various nitrile substrates to generate secondary and tertiary nitriles. Importantly, to the best of our knowledge these are the first examples of C–H bond activation reactions occurring at a NiIII center, which may exhibit different reactivity and selectivity profiles than those corresponding to analogous NiII centers. These studies provide guiding principles to design catalytic C–H activation and functionalization reactions involving high-valent Ni species.