transition metal‐free approach to achieve the selective cleavage of the α‐carbonyl C(sp3)−H bond in alkylesters by using inexpensive, low‐toxic, and insensitive perfluoroalkyl iodide as the radical initiator has been developed. A variety of enamides, N‐heterocycles, amides, thiophenols, and phenols could be successfully incorporated into functionalizedalkyl groups by intermolecular amination, thioetherification