Access to Sterically Hindered Thioethers (α-Thioamides) Under Mild Conditions Using α-Halohydroxamates: Application toward 1,4-Benzothiazinones and 4,1-Benzothiazepinones.

Herein, we report a new and highly efficient approach for synthesizing congested α-thioamides under mild reaction conditions (mild base, room temperature, and short duration) using α-halo hydroxamates as direct alkylating agents. The reaction works well with both (hetero)aryl and alkyl thiols, tolerating a broad functional group and diverse substrate scope, including benzeneselenol for selenoether construction. The strategy enables efficient synthesis of biologically relevant 1,4 benzothiazinone and 4,1-benzothiazepinone cores, along with various other functionalized sulfur-based scaffolds of biological importance.