Having established the optimized conditions, we examined the substrate scope of this transformation (Fig. ). Simple unfunctionalized aromatic and aliphatic alkenes could be smoothly converted to β-chloroketones in 59-80% yields (Fig. ). Various transformable handles, including halides (7, 8), aldehyde (9), ketone (10), ester (11), cyano (12), acid (13), and amide (14) were well tolerated at different positions of the aliphatic chains. The limitation is found for amino or hydroxyl groups present in the alkene. Such substrates undergo direct coupling with the acid chloride employed: 15 was not observed at all, while 17 was obtained only in low yield (25%). Instead, protected amine (NHBoc) and hydroxyl (OTBDMS, OTs) alkene derivatives proceed in good yields (16, 18, and 19). Alkenes bearing heterocycles such as oxirane, carbazole, and phenothiazine moieties were compatible with this transformation (20-22). Boron-and silicon-containing alkenes were also successful, forming the difunctionalized products 23 and 24. Di-and trisubstituted alkenes smoothly afforded the desired products 25 and 26, however, no conversion of the starting material was observed for tetrasubstituted alkenes. Six-to eight-membered cyclic olefins with internal double bond proved to be efficient substrates to give the desired products (27-29) with moderate to excellent diastereoselectivity. The high site selectivity for β-chloroacyl derivatives 26 and 29 may arise from the synergistic steric and stereoelectronic effects upon radical addition. Moreover, exocyclic alkenes exhibited perfect regioselectivity to provide the desired products 30 and 31. To demonstrate the preparative utility of this protocol, β-chloroketones 1 and 30 were synthesized on 5.0 mmol scale without a significant decrease in yield (70% and 58%, respectively; Fig. ).