Umpolung Strategy for Synthesis of β‑Ketonitriles through Hypervalent Iodine-Promoted Cyanation of Silyl Enol Ethers

An efficient method to synthesize β-ketonitriles from silyl enol ethers by an umploung hypervalent iodine­(III)–CN species generated <i>in situ</i> from PhIO/BF₃·Et₂O/TMSCN has been developed for the first time. This method can be applied to structurally diverse aromatic and aliphatic substrates and further extended to preparation of bioactive compounds like 5-aminopyrazole and 5-aminoisoxazole