Photoinduced Difluoromethylation‐Oximation of Alkenes Enabled by Boryl Radical‐Mediated Halogen Atom Transfer

Although ligated boryl radical (LBR)‐mediated halogen atom transfer (XAT) is highly valuable in organic synthesis, its applications remain largely confined to hydrodehalogenation or Giese‐type additions. Herein, we disclose a metal‐ and photocatalyst‐free regioselective difluoromethylation‐oximation of alkenes enabled by tert ‐butyl nitrite (TBN), which acts dually as the oxime source and hydrogen atom transfer (HAT) initiator to drive the LBR‐mediated XAT. This scalable protocol exhibits broad substrate generality and excellent functional group compatibility.