Control experiments revealed that the presence of both B1 and light was essential for the observed reactivity (Table , entries 6 and 7, respectively). Moreover, heating the mixture at 60 °C in the dark or using blue light ( = 456 nm) did not lead to any appreciable amounts of 3 (Table , Entries 8-9). Notably, when the radical acceptor 2a was absent, 1a was partly reduced to cyclohexane (Table , Entry 10), which is in line with previous reports. With these optimized conditions in hand, we moved to evaluate the generality of this photoinduced LBR-mediated hydroalkylation protocol (Figure ). We were pleased to find that a diverse set of primary, secondary and tertiary alkyl iodides were all effective and yielded the targeted adducts in good to excellent isolated yields. Model compound 3 was obtained in 81% yield after isolation. Similarly, compounds 4 and 5 deriving from the reaction between dibutyl maleate (2a) and 2-iodopropane or 2-iodobutane, respectively, were prepared in very good yields (80-87 %). Next, we subjected various primary alkyl iodides to our reaction conditions and found that the length of the alkyl chain did not impact the reactivity: products 6-8 were all obtained in good yields (78-93%). Interestingly, the hydromethylation of olefin 2a (9, 65%) could be realized using an excess of iodomethane. Also, primary organic iodides with substituents in the β-position were activated by the boryl radical and the corresponding adducts could be isolated in good yields (10-11, 55-77%). Notably, 1-chloro-3-iodopropane could be selectively cleaved at C-I bond, yielding adduct 12 in 75% yield. Various tertiary alkyl iodides were also competent reaction partners in our hydroalkylation protocol, resulting in the formation of the corresponding products (13-15, 70-84%).