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 C2-H and C3-H bond activation steps mediated by Ni^III. 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 Ni^III center, which may exhibit different reactivity and selectivity profiles than those corresponding to analogous Ni^II centers. These studies provide guiding principles to design catalytic C-H activation and functionalization reactions involving high-valent Ni species.