Development of catalytic amide bond-forming methods is important because they could potentially address the existing limitations of classical methods using superstoichiometric activating reagents. In this paper, we disclose an Umpolung amidation reaction of carboxylic acids with nitroarenes and nitroalkanes enabled by the triplet synergistic catalysis of FeI₂, P(V)/P(III) and photoredox catalysis, which avoids the production of byproducts from stoichiometric coupling reagents. A wide range of carboxylic acids, including aliphatic, aromatic and alkenyl acids participate smoothly in such reactions, generating structurally diverse amides in good yields (86 examples, up to 97% yield). This Umpolung amidation strategy opens a method to address challenging regioselectivity issues between nucleophilic functional groups, and complements the functional group compatibility of the classical amidation protocols. The synthetic robustness of the reaction is demonstrated by late-stage modification of complex molecules and gram-scale applications.

催化酰胺键形成方法的开发很重要，因为它们可以潜在地解决使用超化学计量活化剂的经典方法的现有局限性。在本文中，我们公开了通过 FeI ₂的三重协同催化实现的羧酸与硝基芳烃和硝基烷烃的 Umpolung 酰胺化反应, P(V)/P(III) 和光氧化还原催化，可避免化学计量偶联剂产生副产物。包括脂肪族、芳香族和烯基酸在内的多种羧酸都能顺利参与此类反应，以良好的产率生成结构多样的酰胺（86 个实例，产率高达 97%）。这种 Umpolung 酰胺化策略开辟了一种解决亲核官能团之间具有挑战性的区域选择性问题的方法，并补充了经典酰胺化方案的官能团兼容性。复杂分子的后期修饰和克级应用证明了该反应的合成稳定性。