On the basis of this work, we have ascertained that ligated borane B1 is capable of promoting radical hydroalkylation via XAT using UV-A to trigger the radical process. Next, we aimed to extend the methodology to visible-light irradiation, which would provide milder reaction conditions and thus a higher functional group tolerance and broader scope. However, as shown before (Table ), blue-light irradiation alone could not initiate the desired reactivity. Consequently, we anticipated that the use of a photoredox catalyst was required. This photocatalyst could absorb the visible light and subsequently generate the LBR via a SET followed by deprotonation. The resulting boryl radical would be ultimately entrusted with the XAT step. Indeed, the oxidation potential of B1 (E(B1 •+ /B1)) has been reported to be +0.76 V vs SCE, which suggests that this approach should be feasible in combination with routinelyused photoredox catalysts.