Controllable Chemodivergent Synthesis of α‐Trifluoromethyl Boronates and gem ‐Difluoroalkenyl Boronates via Photoredox 1,2‐Boron Migratory Carbonylation

Comprehensive Summary Fluorinated organoborons are highly valuable building blocks in drug discovery and materials science. However, the direct and step‐economic synthesis of these complex structures remains a major challenge. Herein, we report a visible‐light‐driven, transition‐metal‐free chemodivergent borocarbonylation of α ‐trifluoromethyl styrenes. This multicomponent platform precisely controls the ultimate fate of the transient α ‐CF 3 benzylic radical. Under catalyst‐free conditions, an electron donor‐acceptor (EDA) complex with Hantzsch ester drives the radical cascade and a subsequent hydrogen atom transfer (HAT) to yield α ‐trifluoromethyl boronates. Alternatively, an Eosin Y/PMP photoredox system promotes a single‐electron transfer (SET) and subsequent β ‐fluoride elimination to afford gem ‐difluoroalkenyl boronates. Overall, this strategy successfully manages the kinetic challenges of multi‐step radical trapping, providing a practical and programmable platform to construct densely functionalized fluorinated organoborons.