The presence of iodine radicals can also enable H-atom abstraction via an open shell mechanism as observed in literature. Further evidence of homolytic cleavage comes from the detection of iodine and the triiodide salt (35). This occurs via iodine radical recombination and subsequent salt quenching of iodine by the base. The overarching goal of this study was to develop a mild photocatalyst free method for the generation of αboryl radicals, with the vision to easily pair this activation mode with other catalysis paradigms. Given the synthetic utility of the generated E-allylic boronic esters, we anticipated that merging our protocol with photocatalytic energy transfer would enable the efficient translation to corresponding Z-isomer via geometric isomerisation (Scheme 3). The realisation of which would provide the user with stereodivergent access to both isomers, significantly expanding the accessible chemical space. Optimisation identified Ir(p-CF3)3 as a suitable sensitiser enabling the reaction to be run at longer wavelength (440 nm) and shorter reaction times (See SI for full details). Intriguingly, reaction efficiency was contingent on catalyst triplet energies and not photoredox properties, as determined by catalyst screening and cyclic voltammetry analysis. The developed conditions enabled reactivity with both electron-rich (Z- [a] Reactions were performed in MeCN on a 0.2 mmol scale using α-iodo BPin (1 equiv.), styrene (3 equiv.), 2,6-lutidine (1.5 equiv.), Ir(p-CF3)3 (1 mol%) under 440 nm irradiation. NMR yield and E:Z ratio was determined by 1 H NMR spectroscopy against a known internal standard (1,3,5-trimethoxybenzene). To aid characterisation of isolated material, the Z-isomer was isolated after in situ oxidation to the corresponding allylic alcohol; [b] The Z-isomer was isolated as the boronic acid, pinacol ester; [c] 2,6-dtbpy (1.5 equiv.) was used.