A mild, organophotocatalytic N–O bond cleavage of Weinreb amides is disclosed, thereby expanding the chemistry of this venerable motif beyond acylation. This redox neutral process begins to reconcile the ubiquity of N–O bonds in contemporary synthesis with the disproportionately harsh, stoichiometric conditions that are often required for bond cleavage. The strategy is compatible with the parent alkyl derivatives (N–OMe, N–OAlkyl), thereby complementing tailored O-substituent approaches that require N–OAr groups (Ar = electron-deficient). A broad range of acyclic and cyclic derivatives are disclosed (>40 examples, up to 95%), and the synthetic utility of the method is demonstrated in a range of applications. In the case of cyclic Weinreb amide derivatives, this platform enables ambiphilic amide aldehydes, of varying chain lengths, to be generated in a single transformation. Inspired by Emil Fischer’s seminal 1908 synthesis of aminoacetaldehyde using sodium amalgam, this method provides a milder route to access this important class of materials. Mechanistically guided reaction development demonstrates the involvement of a photoinduced electron transfer (PET) mechanism, and this has been further advanced to a consecutive photoinduced electron transfer (ConPET) manifold: this has significantly expanded the scope of compatible substrates.

中文翻译：

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Weinreb 酰胺的有机光催化 N-O 键断裂：从 PET 到 ConPET 平台的机制引导进化

Weinreb 酰胺的温和、有机光催化 N-O 键裂解，从而将这一古老基序的化学扩展到酰化之外。这种氧化还原中性过程开始调和当代合成中普遍存在的 N-O 键与键断裂通常所需的不成比例的苛刻化学计量条件。该策略与母体烷基衍生物（N-OMe、N-OAlkyl）兼容，从而补充了定制的O- 需要 N-OAr 基团的取代基方法（Ar = 缺电子）。公开了广泛的无环和环状衍生物（>40 个实例，高达 95%），并且该方法的合成效用在一系列应用中得到证明。在环状 Weinreb 酰胺衍生物的情况下，该平台能够在一次转化中生成不同链长的两亲酰胺醛。受 Emil Fischer 1908 年使用钠汞齐合成氨基乙醛的开创性启发，这种方法提供了一种更温和的途径来获得这类重要的材料。机械引导的反应发展证明了光诱导电子转移 (PET) 机制的参与，这已进一步发展为连续光诱导电子转移 (ConPET) 歧管：