Oxy‐Borylenes as Photoreductants: Synthesis and Application in Dehalogenation and Detosylation Reactions

While the range of accessible borylenes has significantly broadened over the last decade, applications remain limited. Herein, we present tricoordinate oxy‐borylenes as potent photoreductants that can be readily activated by visible light. Facile oxidation of CAAC stabilized oxy‐borylenes (CAAC)(IPr(2)Me(2))BOR (R=TMS, CH(2)CH(2)C(6)H(5), CH(2)CH(2)(4‐F)C(6)H(4)) to their corresponding radical cations is achieved with mildly oxidizing ferrocenium ion. Cyclovoltammetric studies reveal ground‐state redox potentials of up to −1.90 V vs. Fc(+/0) for such oxy‐borylenes placing them among the strongest organic super electron donors. Their ability as photoreductants is further supported by theoretical studies and showcased by the application as stoichiometric reagents for the photochemical hydrodehalogenation of aryl chlorides, aryl bromides and unactivated alkyl bromides as well as the detosylation of anilines.