Ru‐catalyzed Formation of Thiosilanes and Selenosilanes using Dichalcogenides as a User‐Friendly Alternative to Thiols and Selenols

AbstractA ruthenium‐catalyzed reaction for the selective transformation of disulfides (and diselenides) into their silyl (and germyl) counterparts has been developed, as the first example of a thiol/thiolate‐free protocol. Our strategy employs commercially available ruthenium dodecacarbonyl as the catalyst in combination with user‐friendly hydrosilanes (and hydrogermanes) and odorless dichalcogenides (S, Se). Further derivatization of heteroaryl halides into unsymmetrical sulfides demonstrated the synthetic potential of the obtained silylthioethers.