Scanning nitrogen in sp3-rich scaffolds enabled by carbonyl-to-nitrogen atom swap.

-rich scaffolds enabled by the exchange of a carbonyl group with an amine moiety, formally achieving a carbonyl-to-nitrogen (CO-to-N) atom swap. Because ketone positional isomers can be readily obtained through carbonyl transposition or carbon-hydrogen oxidation from a common carbocyclic precursor, the CO-to-N atom swap greatly streamlines the preparation of SNH positional analogs and obviates the need for multiple de novo syntheses. The CO-to-N reaction exhibits exceptional functional group compatibility and generality, which makes it well suited for late-stage modification of complex bioactive molecules and for isotopic labeling.