Thermal Rearrangement of the S–N Bond of Thiooxime Esters

The labile O-N bond of oxime esters has enabled versatile access to many heterocyclic scaffolds. Alternatively, the analogous chemistry for thiooxime esters, which contain an S-N bond, has not been explored. Herein, we interrogate the reactivity of thiooxime esters and identify a homolytic fragmentation and rearrangement mechanism. This work provides the first exploration of the reactivity of this S-N functional group.