Sulfenylnitrene-Mediated Nitrogen-Atom Insertion into Pyrroles, Indoles, and Imidazoles

In this study, we harness the distinct reactivity of sulfenylnitrenes, which insert a single nitrogen atom to transform readily available pyrroles, indoles, and imidazoles into synthetically challenging pyrimidines, quinazolines, and triazines, respectively. Our additive-free method for skeletal editing employs easily accessible, benchtop-stable sulfenylnitrene precursors as a source of a single nitrogen atom. This chemical approach is compatible with free pyrroles, indoles, and imidazoles with diverse functional groups, including oxidation-sensitive functionalities like phenol and thioether. Additionally, this approach facilitates the selective incorporation of a single nitrogen atom into various natural products, amino acids, and pharmaceuticals. Furthermore, we have conducted mechanistic studies and explored regioselectivity outcomes through DFT calculations.