Having established a set of general reaction conditions, the scope and limitations were established (Scheme 2). Pleasingly, the protocol was amenable to a range of styrenes including electron-rich (E-1, E-5, and E-6) and electron-neutral systems (E-4 and E-12) which favoured the E-isomer in good yield and selectivity. Intriguingly, electron-rich heterocycles, typically prone to reactivity with electron-deficient radicals, were also permitted (E-8, E-16, and E-18). Furthermore, while electron-deficient halides (E-10 and E-11) were tolerated as styrene coupling partners, mesomerically electron-withdrawing groups led to depreciated yields (< 40% NMR yield, see SI for full details), presumably due to a mismatch in radical philicity with the electron deficient α-boryl radical. The α-phenyl derivative (9), was isolated in 80% yield, while ortho-substituted examples (E-12) also proved to be effective. The reaction was very much tolerant of modifications to the α-iodo boronic ester, enabling efficient reactivity with secondary (E-10 to E-14), tertiary (E-15 to E-18) and quaternary (E-19) precursors. It is pertinent to note, increased substitution (E-19) required an increase in reaction temperature for appreciable coupling. Intermolecular radical traps could be efficiently extended to silyl enol ethers enabling the rapid generation of β-boryl ketones (20 and 21). Finally, expansion of the scope to common, biologically relevant frameworks included a modified estrone derivative (E-22), D-galactose derivative (E-23) and the sterically encumbered natural product-derived tocopherol example (E-24). Despite concerted efforts, nonstyrenyl systems were found to be unreactive under model reaction conditions (see SI for full details).