Photogeneration of α-Bimetalloid Radicals via Selective Activation of Multifunctional C1 Units

Light-driven strategies that enable the chemoselective activation of a specific bond in multifunctional systems are comparatively underexplored in comparison to transition-metal-based technologies, yet desirable when considering the controlled exploration of chemical space. With the current drive to discover next-generation therapeutics, reaction design that enables the strategic incorporation of an sp³ carbon center, containing multiple synthetic handles for the subsequent exploration of chemical space would be highly enabling. Here, we describe the photoactivation of ambiphilic C1 units to generate α-bimetalloid radicals using only a Lewis base and light source to directly activate the C-I bond. Interception of these transient radicals with various SOMOphiles enables the rapid synthesis of organic scaffolds containing synthetic handles (B, Si, and Ge) for subsequent orthogonal activation. In-depth theoretical and mechanistic studies reveal the prominent role of 2,6-lutidine in forming a photoactive charge transfer complex and in stabilizing in situ generated iodine radicals, as well as the influential role of the boron p-orbital in the activation/weakening of the C-I bond. This simple and efficient methodology enabled expedient access to functionalized 3D frameworks that can be further derivatized using available technologies for C-B and C-Si bond activation.