Controlling Selectivity in Shuttle Hetero‐difunctionalization Reactions: Electrochemical Transfer Halo‐thiolation of Alkynes

Shuttle hetero‐difunctionalization reaction, in which two chemically distinct functional groups are transferred between two molecules, has long been an unmet goal due to the daunting challenges in controlling the chemo‐, regio‐, and stereoselectivity. Herein, we disclose an electrochemistry enabled shuttle reaction (e‐shuttle) to selectively transfer one RS(−) and one X(−) group between β‐halosulfides and unsaturated hydrocarbons via a consecutive paired electrolysis mechanism. The preferential anodic oxidation of one anion over the other, which is controlled by their distinct redox potentials, plays a pivotal role in controlling the high chemoselectivity of the process. This easily scalable methodology enables the construction of a myriad of densely functionalized β‐halo alkenyl sulfides in unprecedented chemo‐, regio‐, and stereoselectivity using benign surrogates, e.g., 2‐bromoethyl sulfide, avoiding the handling of corrosive and oxidative RS–Br reagents. In a broader context, these results open up new strategies for selective shuttle difunctionalization reactions.