PhotoinducedAssembly of Diverse Homoallylic Boronatesfrom <i>gem</i>-Diborons

In comparison to alkyl monoboron or 1,2-diboron, which can generate alkyl radicals via tetracoordinate boron species under photocatalytic conditions, the participation of <i>gem</i>-diborons as substrates in such reactions remains to be developed. Herein, we report a method utilizing <i>gem</i>-diborons as starting materials to generate α-boryl radicals, which then react with various olefins, successfully and efficiently constructing a diverse range of high-value homoallylic boronates; meanwhile, the <i>gem</i>-difluorohomoallylic skeletons could also be smoothly obtained. This transformation demonstrates broad substrate scope and excellent tolerance toward functional groups, enhancing the utility of <i>gem</i>-diboron as precursors for C–C bond construction and the production of valuable products.