Galloway Jordan D, Sarabia Cristian, Fettinger James C, Hratchian Hrant P, Baxter Ryan D
Department of Chemistry and Chemical Biology, University of California, Merced, Merced, California 95343, United States.
Department of Chemistry, University of California, Davis, Davis, California 95616, United States.
Org Lett. 2021 May 7;23(9):3253-3258. doi: 10.1021/acs.orglett.1c00637. Epub 2021 Apr 12.
Here we report a new chemical reagent for transnitrosation under mild experimental conditions. This new reagent is stable to air and moisture across a broad range of temperatures and is effective for transnitrosation in multiple solvents. Compared with traditional nitrosation methods, our reagent shows high functional group tolerance for substrates that are susceptible to oxidation or reversible transnitrosation. Several challenging nitroso compounds are accessed here for the first time, including N isotopologues. X-ray data confirm that two rotational isomers of the reagent are configurationally stable at room temperature, although only one isomer is effective for transnitrosation. Computational analysis describes the energetics of rotamer interconversion, including interesting geometry-dependent hybridization effects.
