Gu Xiang, Wang Taoyong, Yan KaKing
School of Physical Science and Technology, ShanghaiTech University, 201210 Shanghai, China.
Org Lett. 2023 Oct 13;25(40):7287-7292. doi: 10.1021/acs.orglett.3c02480. Epub 2023 Oct 3.
An environmentally friendly new C-H alkylation method of N-heteroarenes facilitated by mechanochemistry is described. Under solvent-free ball-milling, mechanoradicals (SO) were generated from persulfate via homolysis in the solid state, at as low as -50 °C. These highly oxidizing radicals readily transform alkyl trifluoroborate salts to their corresponding carbon-based radicals for subsequent C-C bond formation with N-heterocycles. Mechanistic studies unambiguously confirmed the involvement of both oxygen- and alkyl-radical-based intermediates.
描述了一种通过机械化学促进的N-杂芳烃的环境友好型新型C-H烷基化方法。在无溶剂球磨条件下，过硫酸盐在固态中通过均裂在低至-50°C的温度下产生机械自由基（SO）。这些高氧化性自由基很容易将烷基三氟硼酸盐转化为相应的碳基自由基，以便随后与N-杂环形成C-C键。机理研究明确证实了基于氧自由基和烷基自由基的中间体均参与其中。
