Fluorine is one of the most important elements that could be installed onto hydrocarbon frameworks in pharmaceuticals, agrochemicals, and materials science. Particularly, in medicinal chemistry, fluorine has been incorporated into drug molecules to improve their liposolubility and metabolic stability. The effect of fluorine atoms in molecules has been well-studied, and in turn, fluorination methodology has flourished as well. One of the most conventional ways to achieve fluorination is electrophilic fluorination. Nucleophiles used in electrophilic fluorinations can be broadly classified into carbanions (e.g., 1,3-dicarbonyls), electron-rich unsaturated bonds (e.g., alkenes and alkynes), and aromatics. However, in these existing methods, fluorination proceeds while retaining the carbon skeleton of the starting material, and fluorinations involving skeletal transformations are rare.