This review summarizes the progress in the fluorination and fluoroalkylation of electron‐rich systems with diverse fluorine (F) and fluoroalkyl (R_fn) reagents employing hypervalent iodine compounds as initiators in the last few decades. Because of the strong electrophilicity, high oxidizing properties, low toxicity, air and moisture stability, ready availability, ease of handling, and mild reaction conditions, the hypervalent iodine reagents have been widely utilized in modern organic chemistry. In particular, the use of hypervalent iodine reagents to initiate the C−F and C−R_fn (R_fn=CF₂H, CF₃, perfluoroalkyl, OCH₂CF₃, SCF₃, SeCF₃ and etc) bond formation has been increasingly developed. In these reactions, hypervalent iodine compounds behave as powerful oxidants or electrophiles and activate the fluorination/fluoroalkylation reagents, the transition‐metal catalysts, or the substrates to in situ form electrophilic or radical intermediates, which subsequently participate in fluorination, difluoromethylation, trifluoromethylation, perfluoroalkylation, trifluoroethoxylation, fluoroalkylthiolation, trifluoromethylselenolation and others under mild conditions. Although great achievements have been made in this area, they are just the initial phase and still require a wide scope for improvement. It is anticipated that this review will draw much attention from the organic chemistry community and inspire more contributions in the development of new hypervalent‐iodine‐mediated fluorination and fluoroalkylation reactions.

中文翻译：

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高价碘试剂介导的氟化和氟烷基化反应

这篇综述总结了过去几十年来使用高价碘化合物作为引发剂的各种氟（F）和氟烷基（R _fn）试剂在富电子体系的氟化和氟代烷基化方面的进展。由于强亲电性，高氧化性，低毒性，空气和湿气稳定性，易于获得，易于操作以及温和的反应条件，高价碘试剂已被广泛用于现代有机化学中。特别地，使用高价碘的试剂来引发CF和C-R _FN（R _FN = CF ₂ H，CF ₃，全氟烷基，OCH ₂ CF ₃，SCF ₃，SECF₃等）键的形成已日益发展。在这些反应中，高价碘化合物表现为强氧化剂或亲电和激活氟化/氟烷基化试剂，在过渡金属催化剂，或底物原位形成亲电子或自由基中间体，它们随后在温和条件下参与氟化，二氟甲基化，三氟甲基化，全氟烷基化，三氟乙氧基化，氟代烷基硫代化，三氟甲基硒代化等。尽管在这方面已经取得了巨大的成就，但它们只是起步阶段，仍然需要广泛的改进空间。预期该综述将引起有机化学界的广泛关注，并在开发新的高价碘介导的氟化和氟代烷基化反应中激发更多的贡献。