Xie Katherine A, Bednarova Eva, Joe Candice L, Sherwood Trevor C, Welin Eric R, Rovis Tomislav
Department of Chemistry, Columbia University, New York, New York 10027, United States.
Chemical Process Development, Bristol Myers Squibb, 1 Squibb Drive, New Brunswick, New Jersey 08903, United States.
J Am Chem Soc. 2024 Sep 18;146(37):25780-25787. doi: 10.1021/jacs.4c08375. Epub 2024 Sep 5.
Carboxylic acids and their derivatives are powerful building blocks in dual Ir/Ni metallaphotoredox methods of decarboxylative arylation due to their abundance as feedstock compounds. However, the library of accessible carboxylic acids is limited by trends in radical stability, often necessitating the development of specific systems for challenging substrates. Herein, we disclose the application of a new Ir(III) photocatalyst and low-energy orange light Ir/Ni metallaphotoredox system with broad applicability in activating both native carboxylic acids and redox-active esters (RAEs). This method represents the first known example of complementary oxidative and reductive decarboxylative paradigms with broadly similar reaction conditions, unlocking the reactivity for challenging substrates. We further show a wide scope of aryl halide and acid coupling partners in both regimes, with added advantages over blue-light-catalyzed aryl alkylation for photosensitive substrates.
羧酸及其衍生物作为原料化合物来源丰富，是双铱/镍金属光氧化还原脱羧芳基化方法中强大的构建模块。然而，可利用的羧酸库受到自由基稳定性趋势的限制，通常需要针对具有挑战性的底物开发特定体系。在此，我们披露了一种新型铱(III)光催化剂和低能量橙色光铱/镍金属光氧化还原体系的应用，该体系在活化天然羧酸和氧化还原活性酯(RAEs)方面具有广泛适用性。此方法代表了首个已知的在大致相似反应条件下互补的氧化和还原脱羧模式的例子，开启了具有挑战性底物的反应活性。我们进一步展示了在这两种模式下芳基卤化物和酸偶联伙伴的广泛范围，相较于蓝光催化的芳基烷基化反应，对光敏底物具有额外优势。
