Pyridine‐2‐Sulfinate as a Bifunctional SO 2 Transfer Reagent; Unlocking Structurally Diverse, Ortho ‐Functionalized Masked Sulfinates

Masked sulfinates have emerged as versatile intermediates in sulfur(VI) chemistry. Although SO 2 ‐transfer reagents enable their direct installation onto arenes, their coupling to sterically hindered ortho ‐substituted aryl halides remains broadly inefficient. Herein, we report the commercially available sodium 2‐pyridylsulfinate (2‐SO 2 Py‐Na) as a simple and efficient SO 2 ‐transfer reagent for installing the 2‐pyridylsulfone (2‐SO 2 Py) group onto aryl iodides and bromides. Rather than overcoming this limitation through direct coupling of ortho ‐substituted substrates, the 2‐SO 2 Py auxiliary enables a complementary route to ortho ‐functionalized products through directed C─H functionalization prior to sulfinate release. This strategy provides modular access to ortho ‐substituted sulfonyl derivatives, including sulfonyl fluorides.