Redox-Neutral TEMPO Catalysis: Direct Radical (Hetero)Aryl C-H Di- and Trifluoromethoxylation.,Angewandte Chemie International Edition

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Redox-Neutral TEMPO Catalysis: Direct Radical (Hetero)Aryl C-H Di- and Trifluoromethoxylation.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-08-23 , DOI: 10.1002/anie.202009490
Johnny W Lee ₁ , Sanghyun Lim ₁ , Daniel N Maienshein ₂ , Peng Liu ₂ , Ming-Yu Ngai ₁

Affiliation

Applications of TEMPO^. catalysis for the development of redox‐neutral transformations are rare. Reported here is the first TEMPO^.‐catalyzed, redox‐neutral C−H di‐ and trifluoromethoxylation of (hetero)arenes. The reaction exhibits a broad substrate scope, has high functional‐group tolerance, and can be employed for the late‐stage functionalization of complex druglike molecules. Kinetic measurements, isolation and resubjection of catalytic intermediates, UV/Vis studies, and DFT calculations support the proposed oxidative TEMPO^./TEMPO⁺ redox catalytic cycle. Mechanistic studies also suggest that Li₂CO₃ plays an important role in preventing catalyst deactivation. These findings will provide new insights into the design and development of novel reactions through redox‐neutral TEMPO^. catalysis.

中文翻译：

氧化还原中性 TEMPO 催化：直接自由基（杂）芳基 CH 二氟甲氧基化和三氟甲氧基化。

TEMPO 的应用^。氧化还原中性转化发展的催化作用很少见。这里报道的是第一个TEMPO ^。（杂）芳烃的催化氧化还原中性 C−H 二氟甲氧基化和三氟甲氧基化。该反应表现出广泛的底物范围，具有较高的官能团耐受性，可用于复杂药物分子的后期功能化。动力学测量、催化中间体的分离和重新研究、UV/Vis 研究和 DFT 计算支持了所提出的氧化 TEMPO ^。/TEMPO ⁺氧化还原催化循环。机理研究还表明Li ₂ CO ₃在防止催化剂失活方面发挥着重要作用。这些发现将为通过氧化还原中性 TEMPO 设计和开发新型反应提供新的见解^。催化。

更新日期：2020-08-23

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