Reductive Cleavage of Unactivated Carbon-Cyano Bonds under Ammonia-Free Birch Conditions.

A general protocol for the reductive cleavage of unactivated carbon-cyano bonds in aliphatic nitriles has been achieved under single-electron-transfer conditions using Na/15-crown-5/HO. Electron is supplied by the electride derived from bench-stable sodium dispersions and recoverable 15-crown-5. HO provides the proton source and suppresses the reduction of aromatic moieties. Compared with the Na/NH electride system generated under traditional Birch conditions, this ammonia-free electride system is more practical and features better reactivity and chemoselectivity for the decyanations of a broad range of aliphatic nitriles.