Das Anuvab, Maher Andrew G, Telser Joshua, Powers David C
Department of Chemistry , Texas A&M University , College Station , Texas 77843 , United States.
Department of Chemistry and Chemical Biology , Harvard University , Cambridge , Massachusetts 02138 , United States.
J Am Chem Soc. 2018 Aug 22;140(33):10412-10415. doi: 10.1021/jacs.8b05599. Epub 2018 Aug 7.
Rh-catalyzed C-H amination is a powerful method for nitrogenating organic molecules. While Rh nitrenoids are often invoked as reactive intermediates in these reactions, the exquisite reactivity and fleeting lifetime of these species has precluded their observation. Here, we report the photogeneration of a transient Rh nitrenoid that participates in C-H amination. The developed approach to Rh nitrenoids, based on photochemical cleavage of N-Cl bonds in N-chloroamido ligands, has enabled characterization of a reactive Rh nitrenoid by mass spectrometry and transient absorption spectroscopy. We anticipate that photogeneration of metal nitrenoids will contribute to the development of C-H amination catalysis by providing tools to directly study the structures of these critical intermediates.
铑催化的C-H胺化反应是一种用于有机分子氮化的强大方法。虽然铑氮宾通常被认为是这些反应中的活性中间体，但这些物种的高反应活性和短暂寿命使得它们难以被观测到。在此，我们报道了一种参与C-H胺化反应的瞬态铑氮宾的光生成。基于N-氯酰胺配体中N-Cl键的光化学裂解而开发的铑氮宾制备方法，使得通过质谱和瞬态吸收光谱对活性铑氮宾进行表征成为可能。我们预计，金属氮宾的光生成将通过提供直接研究这些关键中间体结构的工具，推动C-H胺化催化的发展。
