Introducing I/formic acid as a green reagent for the reduction of sulfinates and sulfoxides

We present a convenient and efficient deoxygenation method for synthesizing disulfides and thioethers. The reaction involves an iodide-catalyzed reduction of methyl sulfinates or sulfoxides, respectively, employing formic acid as a stoichiometric reductant. The methodology demonstrates excellent yields and remarkable orthogonality towards other reducible functional groups. In silico explorations revealed the synergistic action of formic acid and in situ generated hydroiodic acid as Brønsted donors within a formic acid framework. This molecular arrangement activates the sulfinyl group and promotes subsequent deoxygenation. Notably, this approach enables the deoxygenation of sulfur-based functional groups using formic acid as the stoichiometric reductant without needing transition metals or strong acidic media such as hydroiodic acid. Overall, this methodology contributes to the advancement of the reduction of diverse oxygenated sulfur-containing compounds in a sustainable approach. A sustainable method using formic acid and iodide as a catalyst for sulfinyl group deoxygenation in sulfoxides and sulfinates. Formic acid networks facilitate sulfinyl reduction.