Synthesis of Tertiary Benzylic Nitriles via Nickel-Catalyzed Markovnikov Hydrocyanation of α-Substituted Styrenes.

The Markovnikov hydrocyanation of α-substituted styrenes enables the synthesis of tertiary benzylic nitriles under nickel catalysis. The Lewis-acid-free transformation features an unprecedented functional groups tolerance, including the -OH and -NH2 groups. A broad range of tertiary benzylic nitriles were obtained in good to excellent yields. In addition, an asymmetric version of this reaction was preliminarily investigated.