高价 Cu(III)−CF3 化合物选择性分子间双氨基-三氟甲基化烯烃,Advanced Synthesis & Catalysis

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高价 Cu(III)−CF3 化合物选择性分子间双氨基-三氟甲基化烯烃
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2022-10-17 , DOI: 10.1002/adsc.202200945
Ning Chen ₁ , Song-Lin Zhang ₂

Affiliation

开发了烯烃的选择性分子间氨基-三氟甲基化，以产生一系列具有生物活性的 β-三氟甲基胺。该方法利用关键的高价 Cu(III)-CF ₃络合物作为 CF ₃自由基和 Cu(II) 氧化剂的组合来源，通过均裂 Cu(III)-CF ₃键断裂。_{CF 3}的这种独特模式自由基生成不同于目前主要依赖光氧化还原催化或使用牺牲自由基引发剂的主要方法。这是一个显着的优势，它大大简化了反应条件，带来了操作上的便利，有利于在其他更复杂的条件下抑制各种副反应。在原位 Cu(II) 氧化剂的帮助下，CF ₃自由基与烯烃加成生成的叔烷基自由基与胺反应，从而能够形成 C-N。该反应显示出良好的化学和区域选择性，抑制了许多潜在的副反应。自由操作现成的 Cu(III)−CF ₃烯烃和苯胺的化合物和原料化合物大大拓宽了反应范围。良好的化学选择性和区域选择性以及操作便利性使该反应从合成的角度来看具有吸引力。本研究中公开的高价 Cu(III)-CF ₃化合物的反应性可用于开发其他有趣的反应，并丰富目前未开发的 Cu(III) 化学。

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Selective Intermolecular Dual Amino-Trifluoromethylation of Alkenes by High-Valent Cu(III)−CF3 Compounds

A selective intermolecular amino-trifluoromethylation of alkenes is developed to produce a range of biologically active β-trifluoromethyl amines. This method exploits a crucial high-valent Cu(III)−CF₃ complex as a combined source of CF₃ radical and Cu(II) oxidant through homolytic Cu(III)−CF₃ bond cleavage. This unique mode of CF₃ radical generation is distinct from current dominant methods that rely largely on photoredox catalysis or the use of sacrificing radical initiator. This represents a significant advantage in that it greatly simplifies the reaction conditions, brings about operational convenience, and is beneficial to suppress various side reactions under otherwise more complicated conditions. A tertiary alkyl radical generated from addition of CF₃ radical to alkenes is proposed to react with amines to enable C−N formation with the assistance of in-situ Cu(II) oxidant. This reaction shows good chemo- and regio-selectivity, suppressing a number of potential side reactions. The free manipulation of readily available Cu(III)−CF₃ compound and feedstock compounds of alkenes and anilines greatly broadens the reaction scope. The good chemo- and regioselectivity, and operational convenience make this reaction attractive from the synthetic viewpoint. The reactivity of high-valent Cu(III)−CF₃ compounds disclosed in this study may be exploited to develop other interesting reactions, and to enrich the currently underdeveloped Cu(III) chemistry.

更新日期：2022-10-17

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