Department of Chemistry, New York University, New York, New York 10003, United States.
J Am Chem Soc. 2023 Feb 8;145(5):2794-2799. doi: 10.1021/jacs.2c13502. Epub 2023 Jan 25.
A photoexcited-nitroarene-mediated anaerobic C-H hydroxylation of aliphatic systems is reported. The success of this reaction is due to the bifunctional nature of the photoexcited nitroarene, which serves as the C-H bond activator and the oxygen atom source. Compared to previous methods, this approach is cost- and atom-economical due to the commercial availability of the nitroarene, the sole mediator of the reaction. Because of the anaerobic conditions of the transformation, a noteworthy expansion in substrate scope can be obtained compared to prior reports. Mechanistic studies support that the photoexcited nitroarenes engage in successive hydrogen atom transfer and radical recombination events with hydrocarbons, leading to -arylhydroxylamine ether intermediates. Spontaneous fragmentation of these intermediates leads to the key oxygen atom transfer products.
报道了一种光激发硝基芳烃介导的脂肪族体系的厌氧 C-H 羟化反应。该反应的成功归因于光激发硝基芳烃的双功能性质，它既是 C-H 键的活化剂，也是氧原子的来源。与以前的方法相比，由于硝基芳烃的商业可用性以及其作为反应唯一介体的特点，这种方法具有成本效益和原子经济性。由于转化是在厌氧条件下进行的，与之前的报道相比，可以获得显著扩大的底物范围。机理研究支持光激发的硝基芳烃与碳氢化合物经历连续的氢原子转移和自由基重组反应，生成 -芳基羟胺醚中间体。这些中间体的自发断裂导致关键的氧原子转移产物的生成。
