With the optimized conditions in hand, we turned our attention to exploring the reaction scope by first varying the Grignard nucleophile (Figure ). A wide range of electron-rich and electron-poor aryl Grignard reagents work well in the reaction with good yields (up to 69% over two steps) and enantioselectivities (up to 91:9 er) that are comparable to the state-of-the-art Fe-catalyzed two component cross-coupling methods. In addition, this method tolerates a range of electronrich and -poor meta-and para-substituents including C-Cl bonds that can be further handles in cross-coupling reactions (10-11). Finally, extended π-systems work well in this transformation albeit modest enantiomeric ratios were observed for some systems (15-18). Notably, x-ray analysis of 18 unambiguously determined the absolute stereochemistry of the major enantiomer as (S). Next, we turned our sights to the radical precursor scope (Figure ). The sterically encumbered cyclic tertiary 1-iodoadamantyl radical precursor provided an improved enantioselectivity (19; 85:15 er) over the acyclic tertiary system using the same Grignard reagent (68:32 er; table 1, entry 2). Further, the tertiary radical precursor bearing an oxygen-containing cyclohexyl ring gave the desired product 20 in good yield and modest enantioselectivity, revealing the potential applicability towards the practical synthesis of heteroatom-containing compounds with relevance to pharmaceutical research. Notably, the reaction was selective towards tertiary alkyl bromides in the presence of other carbon-halogen bonds including C(sp )-Br and primary C(sp 3 )-Cl bonds (21 and 24). In addition, other representative acyclic tertiary alkyl radical precursors, including benzylic systems, yield the desired products in good yields and modest enantioselectivities (22, 23, 25).