Regioselective <i>N</i>‑arylationof <i>N</i>‑Acylsulfenamides Enabled by <i>o</i>‑Quinone Diimides

The functionalization of <i>N</i>-acylsulfenamides is a research focus in organosulfur chemistry, as the <i>N</i>–<i>S</i> array has unique properties and versatile applications. Although great progress has been made in <i>S-</i>functionalization, the <i>N-</i>functionalization, especially the <i>N</i>-arylation of <i>N</i>-acylsulfenamides, has rarely been explored because of the lower nucleophilicity of the <i>N</i>-site. Herein, we report a Brønsted acid-catalyzed regioselective <i>N</i>-arylation reaction of <i>N</i>-acylsulfenamides with <i>o</i>-quinone diimides. Under mild and metal-free conditions, a wide range of <i>N</i>-arylated <i>N-</i>acylsulfenamides have been prepared in good yields with excellent regioselectivity. The ease of gram-scale synthesis and transformations into useful sulfonamides demonstrates their synthetic practicality.