Sportelli Giuseppe, Grando Gaia, Bevilacqua Manuela, Filippini Giacomo, Melchionna Michele, Fornasiero Paolo
Department of Chemical and Pharmaceutical Sciences, University of Trieste, via Licio Giorgieri 1, 34127, Trieste, Italy.
Department of Science, Technology and Society, University School for Advanced Studies IUSS Pavia, Piazza della Vittoria 15, 27100, Pavia, Italy.
Chemistry. 2023 Oct 2;29(55):e202301718. doi: 10.1002/chem.202301718. Epub 2023 Aug 30.
The use of graphitic carbon nitride (g-CN) for the photocatalytic radical formylation of anilines, which represents a more sustainable and attractive alternative to the currently used approaches, is reported herein. Our operationally simple method occurs under mild conditions, employing air as an oxidant. In particular, the chemistry is driven by the ability of g-CN to reach an electronically excited state upon visible-light absorption, which has a suitable potential energy to trigger the formation of reactive α-amino radical species from anilines. Mechanistic investigations also proved the key role of the g-CN to form reactive superoxide radicals from O via single electron transfer. Importantly, this photocatalytic transformation provides a variety of functionalized formamides (15 examples, up to 89 % yield).
本文报道了使用石墨相氮化碳（g-CN）对苯胺进行光催化自由基甲酰化反应，这是一种比目前使用的方法更具可持续性和吸引力的替代方法。我们操作简单的方法在温和条件下进行，使用空气作为氧化剂。特别地，该化学反应是由g-CN在可见光吸收后达到电子激发态的能力驱动的，该激发态具有合适的势能来引发苯胺形成反应性α-氨基自由基物种。机理研究还证明了g-CN通过单电子转移从O2形成反应性超氧自由基的关键作用。重要的是，这种光催化转化提供了多种功能化甲酰胺（15个实例，产率高达89%）。
