Diazocarbonyl compounds are useful substrates in di- and trifunctionalization reactions based on F/CF3/SCF3 introduction. In the presented reactions, various electrophilic F/CF3/SCF3-transfer reagents were used. The majority of the reactions were based on rhodium catalysis and the application of various oxygen nucleophiles, such as alcohols, cyclic/acyclic ethers, and carboxylic acids. The oxyfluorination reactions were further developed to provide a new fluorine-18 labeling method. Density functional theory (DFT) modeling studies were performed to get a deeper mechanistic understanding of these reactions. These DFT modeling studies indicated that the catalytic reactions proceed through formation of rhodium carbene and oxonium ylide intermediates. The oxonium ylides undergo tautomerization to enol ether type species that subsequently react with the electrophilic F/CF3/SCF3-transfer reagents. We also present an arylation–trifluoromethylthiolation reaction for simultaneous introduction of C–SCF3 and C–C bonds into diazocarbonyl compounds. This reaction does not proceed by rhodium catalysis, but follows a Hooz-type mechanism. 1 Introduction 2 Diazocarbonyl Compounds: Versatile Substrates in Organic ­Synthesis 3 Fluorination, Trifluoromethylation, and Trifluoromethylthiolation of Diazo Substrates 3.1 Metal-Free Reactions 3.2 Metal-Catalyzed Reactions with Nucleophilic Reagents 3.3 Metal-Catalyzed Reactions with Electrophilic Reagents 4 Oxyfluorination Reactions 4.1 Fluorobenziodoxole as a Fluorine Source 4.2 [18F]Fluorobenziodoxole as a Fluorine Source for Radiolabeling 4.3 Oxyfluorination with NFSI 5 Oxytrifluoromethylation 6 Oxytrifluoromethylthiolation 7 Arylation–Trifluoromethylthiolation Reaction 8 Conclusions and Outlook

中文翻译：

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有机氟化学中的重氮羰基化合物

在基于 F/CF3/SCF3 引入的双和三官能化反应中，重氮羰基化合物是有用的底物。在所提出的反应中，使用了各种亲电 F/CF3/SCF3 转移试剂。大多数反应基于铑催化和各种氧亲核试剂的应用，例如醇、环状/无环醚和羧酸。氧氟化反应得到进一步发展，以提供一种新的氟 18 标记方法。进行了密度泛函理论 (DFT) 建模研究，以更深入地了解这些反应的机理。这些 DFT 模型研究表明，催化反应是通过形成铑卡宾和氧鎓叶立德中间体来进行的。氧鎓叶立德发生互变异构化为烯醇醚类物质，随后与亲电 F/CF3/SCF3 转移试剂反应。我们还提出了一种芳基化-三氟甲硫基化反应，用于将 C-SCF3 和 C-C 键同时引入重氮羰基化合物中。该反应不是通过铑催化进行，而是遵循 Hooz 型机制。1 介绍 2 重氮羰基化合物：有机合成中的多功能底物 3 重氮底物的氟化、三氟甲基化和三氟甲硫基化 3.1 无金属反应 3.2 与亲核试剂的金属催化反应 3.3 与亲电试剂的金属催化反应 1 氟代烯烃反应 4 氟烯烃反应来源 4.2 [18F] Fluorobenziodoxole 作为放射性标记的氟源 4。