We developed metal- and photosensitizer-free cross-dehydrogenative coupling (CDC) systems to promote the cleavage of strong C(sp³)–H bonds through a distinct non-photoredox engaged hydrogen atom transfer (HAT) process. Mechanistic experiments indicate that this reaction predominantly proceeds through an energy transfer mechanism from excited-state heteroarenes to peroxides, with the direct irradiation of peroxides serving as a supplementary and secondary pathway to promote homolysis of the O–O bond. The resulting oxygen radicals undergo HAT from a substrate C–H bond, followed by addition of the obtained alky radical to heteroarenes, facilitating the formation of the key C–C bond. The conclusion that tert-butyl peroxybenzoate (TBPB) and heteroarenes are the optimal energy transfer pairs was drawn by screening a series of peroxides. In addition to its efficiency and step-economy, this approach boasts environmental advantages, making it suitable for the late-stage functionalization of pharmaceuticals and drug-like molecules, while accommodating a wide range of functional groups.

中文翻译：

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通过光诱导能量转移实现无金属和光敏剂的交叉脱氢偶联

我们开发了不含金属和光敏剂的交叉脱氢偶联（CDC）系统，通过独特的非光氧化还原参与氢原子转移（HAT）过程促进强C（sp ^{3 ）–H键的裂解。}机理实验表明，该反应主要通过从激发态杂芳烃到过氧化物的能量转移机制进行，过氧化物的直接照射作为促进O-O键均裂的补充和次要途径。生成的氧自由基从底物 C-H 键发生 HAT，然后将所得烷基加成到杂芳烃上，促进关键 C-C 键的形成。通过对一系列过氧化物的筛选，得出过苯甲酸叔丁酯（TBPB）和杂芳烃是最佳能量传递对的结论。除了效率和步骤经济性之外，这种方法还具有环境优势，使其适合药物和类药物分子的后期功能化，同时容纳广泛的官能团。