Oxidative activation and reductive formation of C-H bonds are crucial in many chemical, industrial, and biological processes. Reported here is a new strategy for these transformations, using a form of proton-coupled electron transfer (PCET): intermolecular electron transfer coupled to intramolecular proton transfer with an appropriately placed cofactor. In a fluorenyl-benzoate, the positioned carboxylate facilitates rapid cleavage of a benzylic C-H bond upon reaction with even weak 1e^- oxidants, for example, decamethylferrocenium. Mechanistic studies establish that the proton and electron transfer to disparate sites in a single concerted kinetic step, via multi-site concerted proton-electron transfer. This work represents a new elementary reaction step available to C-H bonds. This strategy is extended to reductive formation of C-H bonds in two systems. Molecular design considerations and possible utility in synthetic and enzymatic systems are discussed.

中文翻译：

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利用质子耦合电子转移有效裂解并形成CH键的新策略。

CH键的氧化活化和还原性形成在许多化学，工业和生物过程中至关重要。此处报道的是使用质子偶联电子转移（PCET）形式的这些转化的新策略：分子间电子转移与分子内质子转移以及适当放置的辅因子结合。在一个芴基苯甲酸盐，所述羧酸盐定位便于在反应苄CH键的快速切割用的即使很弱的1 ë ^-氧化剂，例如十甲基二茂铁鎓。机理研究表明，质子和电子通过多位协调的质子-电子转移，在一个一致的动力学步骤中转移到不同的位点。这项工作代表了可用于CH键的新的基本反应步骤。该策略扩展到在两个系统中还原形成CH键。讨论了分子设计方面的考虑以及在合成和酶促体系中的可能用途。