[Structural Optimization in Nitrile Synthesis via Desulfonylative Smiles Rearrangement].

Nitriles are important organic compounds that are frequently found in pharmaceuticals, natural products, agrichemicals, and functional materials. In addition, nitriles serve as versatile building blocks in synthetic chemistry, as the nitrile moiety can be readily transformed into a variety of valuable functional groups, such as carbonyl derivatives, amines, and heterocycles. However, conventional methods for nitrile synthesis often rely on highly toxic metal cyanides, such as copper(I) cyanide (CuCN) and potassium cyanide (KCN). In this review, I introduce our recent works on a cyanide- and transition metal-free approach for the synthesis of (hetero)aromatic and aliphatic nitriles from N-acyl (2-nitrophenyl)sulfonamides via a base-promoted desulfonylative Smiles rearrangement. The reactions proceeded under operationally simple conditions using potassium acetate as a base and 1,3-dimethyl-2-imidazolidinone as a solvent. This method enables the efficient preparation of a wide range of nitriles, including those bearing primary, secondary, and tertiary carbon centers, with broad functional group compatibility and in good to excellent yields.