Selective Phthalimido- N -oxyl (PINO)-Catalyzed C-H Cyanation of Adamantane Derivatives

We present a new method for the selective C(sp(3) )-H cyanation of adamantane derivatives with PINO as the hydrogen abstracting reagent. A cyano radical is thereby transferred from p- toluenesulfonyl cyanide, allowing the cyanation of adamantane derivatives in up to 71% yield. The protocol presents a novel way to orthogonally functionalized adamantanes that are otherwise difficult to prepare. Mechanistic studies support the hypothesis of a radical pathway.