Under non-metallic catalysis and conditions with no external energy input, there remain to date significant unmet challenges in precise C-H functionalization with controllable sites and numbers. Here, by establishing a hierarchical, porous, low N-doped graphitic carbon/hexafluoroisopropanol (HFIP) catalyst system, we report selective construction of structurally novel π-extended N,O-heterocycles from tetrahydroquinoxalines and 2-naphthols via oxidative aryl C-H bifunctionalization at room temperature. There is good substrate and functional group compatibility, as well as excellent step and atom efficiency, and the reaction uses an accessible catalyst and a naturally abundant oxidant. Mechanistic study reveals that the in situ-formed catalyst-O₂ species stabilized by HFIP enables a decent substrate oxidation to match the coupling processes. The work highlights the potential practicality of a strategy merging suitable carbon material and HFIP in further development of oxidative transformations under sustainable catalysis.

在非金属催化和没有外部能量输入的条件下，迄今为止，在具有可控制的位点和数目的精确CH官能化方面仍然存在重大的未解决挑战。在这里，通过建立一个分层的，多孔的，低氮掺杂的石墨碳/六氟异丙醇（HFIP）催化剂体系，我们报道了通过氧化芳基CH双官能团从四氢喹喔啉和2-萘酚选择性地构建结构新颖的π延伸的N，O-杂环的方法。室内温度。具有良好的底物和官能团相容性，以及出色的步骤和原子效率，并且该反应使用可及的催化剂和天然丰富的氧化剂。机理研究表明，原位形成的催化剂O ₂通过HFIP稳定化的各种物质能够使适当的底物氧化，以匹配偶联过程。这项工作强调了将合适的碳材料和HFIP融合的策略在可持续催化作用下进一步发展氧化转化的潜在实用性。