The fluoroalkyl fragment plays a vital role in various fields such as pharmaceuticals and materials science, and has a significant impact on human life not only on the present but also in the future. The insertion of fluoroalkyl groups into the chemical skeletons can cause considerable alternations in the chemical, physical and biological properties of molecules, which has attracted numerous scientists from different fields. This review focuses on N-heterocyclic carbene (NHC)-catalyzed fluoroalkylation reactions, providing a detailed analysis and summary of the achievements in the past two decades. Many successful examples clearly indicate that NHCs can catalyze the tranformation of fluoroalkylation reagents with various electronic characteristics, whether electrophilic, nucleophilic, or radical precursors. Herein, the fluoroalkylation reactions are classified based on different catalytic modes of NHCs: Lewis base catalysis, Umploung catalysis, radical catalysis and others. Meanwhile, by refining and systematically studying the contribution of NHC catalysis in fluoroalkylation reactions, this review is expected to provide valuable insights and enlightenment for related fields.

氟烷基片段在医药、材料科学等各个领域发挥着至关重要的作用，不仅对现在而且对未来的人类生活产生重大影响。在化学骨架中插入氟代烷基可以使分子的化学、物理和生物性质发生相当大的改变，吸引了众多不同领域科学家的关注。本综述重点关注N-杂环卡宾（NHC）催化的氟烷基化反应，对过去二十年取得的成就进行了详细的分析和总结。许多成功的例子清楚地表明NHCs可以催化具有各种电子特性的氟烷基化试剂的转化，无论是亲电的、亲核的还是自由基前体。其中，氟烷基化反应根据NHCs的不同催化方式分为：Lewis碱催化、Umploung催化、自由基催化等。同时，通过提炼和系统研究NHC催化在氟烷基化反应中的贡献，期望为相关领域提供有价值的见解和启示。