We then investigated the substrate scope of aryl cyclopropanes 8 in the 1,3 chlorination (Scheme 3A). The desired products were obtained cleanly, and no aromatic chlorination was observed regardless of the electronic properties of the phenyl ring (products 9a-h). The isolated yield of 9a was only 80% compared to the quantitative NMR yield due to its instability on column chromatography. We encountered similar issues with products 9b and 9c. Product 9b was even fully hydrolyzed on column chromatography to give the corresponding benzylic alcohol in 51% yield. The reaction tolerated various functionalities, including a bromo (9d), a cyanide (9e), an acetyl (9f), a pinacol boronate (9g), and a naphthyl (9h) groups, with isolated yields ranging from 63% to 91%. A diphenyl-substituted cyclopropane resulted in 79% yield of product 9i. A donor-acceptor cyclopropane with a diester functional group delivered 68% of products 9j. Interestingly, the reaction tolerated a carboxylic acid and a pyridine derivative, giving 91% yield of 9k and 74% yield of 9l. It has been reported that pyridines can substitute chloride on 6a, and carboxylic acids are usually incompatible with reactions involving electrophilic HIRs. The products observed demonstrated that photolysis was fast enough to promote the radical pathway over other reactions. The protocol also allowed the late-stage chlorination of heterocyclic bioactive molecules, yielding chlorinated products 9m derived from the drug Lesinurad in 42% yield and 9n in 59% yield. It is worth mentioning that the thioether in 9m was tolerated, even if it could be sensitive to oxidation. Scheme 3. Substrate scope of chlorination. Yields in bracket are NMR yields with CH2Br2 as an internal standard. Scope on 0.2 mmol scale. 1.5 equiv. of 6a. The chlorinated compound was hydrolyzed on reverse phase chromatography, and the corresponding alcohol was isolated. 2.0 equiv. of 6a. 2.5 equiv. of 6a. 4.0 equiv. of 6a.