O-Protected NH-free hydroxylamines: emerging electrophilic aminating reagents for organic synthesis.

In this highlight, O-protected NH-free hydroxylamine derivatives have been evaluated in the construction of nitrogen-enriched compounds, such as primary amines, amides, and N-heterocycles, with high regio-, chemo- and stereoselectivity in the unprotected form, showcasing the late-stage functionalization of natural products, drugs and functional molecules by biocatalysis, organocatalysis, and transition metal catalysis. The reactivity dichotomy among these N-O reagents has been explored based on SET and metal-nitrenoids.