F-Labeling methods for the preparation of F-labeled molecular probes can be classified into electrophilic fluorination, nucleophilic fluorination, metal-F coordination, and F/F isotope exchange. Isotope exchange-based F-labeling methods demonstrate mild conditions featuring water resistance and facile high-performance liquid chromatography-free purification in direct F-labeling of substrates. This paper systematically reviews isotope exchange-based F-labeling methods sorted by the adjacent atom bonding with F, i.e., carbon and noncarbon atoms (Si, B, P, S, Ga, Fe, etc.). The respective isotope exchange mechanism, radiolabeling condition, radiochemical yield, molar activity, and stability of the F-product are mainly discussed for each isotope exchange-based F-labeling method as well as the cutting-edge application of the corresponding F-labeled molecular probes.
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