Having established optimal reaction conditions (Table , Entry 8), our next objective was to assess the scope of the light-mediated B-alkyl SMC reaction (Scheme 2). As expected, aryl bromides with electron-withdrawing groups displayed favorable performance, resulting in good isolated yields for compounds 3-8 (40-78%). Regarding the substitution pattern on the aromatic ring (3-5), we observed that the presence of an ortho substituent led to lower yields. Subsequently, we shifted our attention to electron-rich aryl bromides, known for their reluctance to undergo oxidative addition by the nickel catalyst. Although challenging, we obtained satisfactory yields for compounds 9 and 10 (40-42%). The cross-coupling reaction also tolerated a BPin functional group (compound 11, 65%), providing opportunities for further diversification. Notably, this particular substrate would have posed inherent difficulties for previously developed approaches (Scheme 1B). When subjected to the optimized reaction conditions, 4-bromo-2-chloro-1-fluorobenzene underwent functionalization solely at the C-Br bond, yielding compound 12 in excellent yield (88%). Recognizing the significance of heterocycles in pharmaceutical compound synthesis, we applied our reaction conditions to a wide range of heteroaryl bromides, including pyridines, quinolines, indoles, indazoles, and pyrazolopyridines. All of these substrates yielded the expected products in good to excellent yields (13-25, 34-87%). Next, our focus shifted to the alkyl borane coupling partner, which can be conveniently synthesized on demand through the hydroboration of readily available or easily prepared alkenes with BH3 (known as Brown hydroboration). Upon subjecting alkyl boranes derived from 1,1-disubstituted olefins to the optimized conditions (referred to as Method A in Scheme 3), the desired products were obtained with excellent yields and exhibited high anti-Markovnikov regioselectivity (54-77%, > 20:1 regioisomeric ratio, 26-27). Remarkably, an allyl chloride could also participate in the transformation, resulting in a 47% yield of product 28. Alkyl boranes derived from cycloalkenes underwent smooth arylation, affording products 29 and 30 in very good yields (67-83%), thus demonstrating the compatibility of secondary carbons with the transformation. Notably, even an estradiol derivative served as a suitable substrate under these conditions, leading to the isolation of compound 31 with a 43% yield and exquisite regioselectivity.