AbstractThe mini‐review is focused on application of silver and its compounds in fluoroorganic synthesis, and it reflects immense progress in this field which took place during the last two decades, with additional examples of reactivity of historical importance. Reactions of C−H, C−F, N−H and O−H bond functionalization, as well as catalysis of cycloaddition reactions and intramolecular rearrangement, retro‐rearrangement, and functional group migrations, have been described. Whenever available in original works, the reaction mechanisms were discussed. Since silver may be catalytically active in each of its available oxidation states from (0), via (I) and (II) to (III) with their immensely diverse properties, the organofluorine part is preceded by a brief overview of chemistry of silver in general. Uniqueness of silver among Group 11 elements is highlighted.

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