On the other hand, the α-oxyalkyl radical (2a˙) can be trapped by minor amounts of solubilized Cl2-formed via the anodic oxidation of chloride-resulting in a chloride intermediate (2a-Cl) . Although the intermediate 2a-Cl was not observed in our experiments, it would theoretically lead to the formation of product 3 via nucleophilic substitution, aided by the anomeric effect . Despite extensive efforts, the C(sp 3 )-H heteroarylation method could not be extended to unactivated aliphatic C(sp 3 )-H bonds (see Supporting Information). The fact that these substrates are unreactive suggests that the oxidation from intermediate 2a˙ to 2a + is only realized when the latter is adequately stabilized, as observed with an oxocarbenium ion.