Electroreductive fluoroalkylative heteroarylation of unactivated alkenes via an unconventional remote heteroaryl migration

Perfluoroalkyl-containing organic molecules are important for a wide range of applications in pharmaceuticals and organic func-tional materials. In this study, an unconventional electroreductive fluoroalkylative heteroarylation of unactivated alkenes via a remote heteroaryl migration is developed. A series of heteroaryls can migrate smoothly, and various fluoroalkyls can be introduced into products. Compared with classical thermochemistry and photo-chemistry, electrochemistry uses generation of radicals and subse-quent radical addition to unactivated alkenes, and heteroaryl migra-tion and hydrogen atom abstraction occur in a small reductive area near the cathode. This approach contributes to the broad substrate scope. Deuterium-labeling experiments and density functional the-ory calculations indicate that N,N-dimethylformamide provides hydrogen atoms for the quenching of carbon radicals after migra-tion instead of water or tetrabutylammonium hexafluorophosphate. A migrated benzothiazole moiety can be transformed into a formyl group, and a facile synthesis can generate substituted cyclopenta-none.