Photoinduced Perfluoroalkyloximation of Alkenes with Simple Perfluoroalkyl Halides

Comprehensive Summary In this paper, the difunctionalizative perfluoroalkyloximation of alkenes has been developed for the first time. This photochemical method allows for the synthesis of various perfluoroalkyl ethanone oximes with excellent regioselectivity and good functional group tolerance. Our method employs the most common perfluoroalkyl source, perfluoroalkyl iodides, as Rf reagents. Besides long‐chain perfluoroalkyl groups, this approach could be extended to incorporating additional groups, including trifluoromethyl, difluoromethyl, sulfonyl, and malonate, selectively into olefins, resulting in a range of β‐substituted ethanone oximes. Notably, the potential of this method in the Fukuyama indole synthesis, generating novel 2‐perfluoroalkylated 3‐(α‐oximidobenzyl)indoles via a radical cascade mechanism with 2‐vinylphenylacryloyl isocyanate as the radical acceptor, presents a compelling avenue for drug synthesis. The protocol is efficient, scalable, and useful for late‐stage modification of bioactive molecules. This paper introduces a new difunctionalizative perfluoroalkyloximation method for alkenes, efficiently synthesizing diverse perfluoroalkyl ethanone oximes with high regioselectivity and functional group tolerance. Notably, it shows potential in Fukuyama indole synthesis, creating novel 2‐perfluoroalkylated indoles via a radical cascade. The method is efficient, scalable, and useful for modifying bioactive molecules.