TBAF-Catalyzed Selective Decyanative Protonation of Disubstituted Malononitriles to α,α-Disubstituted Acetonitriles

We report a metal-free, TBAF-catalyzed decyanative protonation of disubstituted malononitriles using phenylsilane as the reducing agent to access α,α-disubstituted acetonitriles. This protocol exhibits mild reaction condition and high chemoselectivity. Its practicality is demonstrated by gram-scale synthesis and diverse downstream transformations, providing an efficient and sustainable approach to nitriles that are valuable in medicinal chemistry and synthetic chemistry.