Selective Nitration and Nitrosation of ArylBoronic Acid Derivatives with <i>N-</i>Nitrososulfonamides

Nitrosoarenes are useful molecules owing to their unique electronic properties. The "NO" functional group is strongly electron-withdrawing, possessing a σ_para value greater than either the nitro or trimethylammonium functional groups. Although many methods exist for the synthesis of nitroarenes, the direct incorporation of the "NO" functional group in a single step to produce nitrosoarenes has historically received less attention. In this paper, we discuss a mild and selective method for the ipso-nitrosation of arylboronic acids and their derivatives. Depending on the substrate identity, both nitro and nitrosoarenes can be formed from arylboronic acids. To overcome substrate-controlled selectivity, we developed a one-pot, two-step procedure to exclusively produce nitrosoarenes from boronic acids with no evidence of unwanted nitroarene products. A variety of arenes and heteroarenes are selectively nitrosated in good yields via reactions run open to air and without protection from moisture.