Solvent‐Enabled Radical Selectivities: Controlled Syntheses of Sulfoxides and Sulfides

Controlling selectivity is of central importance to radical chemistry. However, the highly reactive and unstable radical intermediates make this task especially challenging. Herein, a strategy for taming radical redox reactions has been developed, in which solvent-bonding can alter the reactivity of the generated radical intermediates and thereby drastically alter the reaction selectivity at room temperature. Various β-oxy sulfoxides and β-hydroxy sulfides can be facilely obtained, some of which are difficult to synthesize by existing methods. Notably, neither a metal catalyst nor any further additives are necessary in these processes.