Nickel-catalyzed desulfonative cross-coupling of benzylsulfonyl chlorides with arylsulfonyl chlorides for synthesis of asymmetric thioethers

Abstract

C–S bond formation is of great interest and plays an important role in organic synthesis, material science, and medicinal chemistry. On the other hand, sulfonyl chlorides are inexpensive, readily available, and easily handled reagents. The use of two different types of sulfonyl chlorides to prepare unsymmetrical thioethers has been considered a challenge task. Here, a nickel-catalyzed desulfonative cross-coupling reaction for the synthesis of unsymmetrical thioethers is disclosed. In this reaction, benzylsulfonyl chlorides play a role as the electrophiles, and arylsulfonyl chlorides serve as the sulfur precursors. We demonstrate that arylsulfonyl chlorides reductively couple with electrophilic benzylsulfonyl chlorides through a desulfonylation process, giving a variety of asymmetric thioethers in moderate-to-excellent yields with good functional group tolerance. By employing readily available sulfonyl chlorides as both electrophiles and sulfur surrogates, we address a challenge in organic synthesis.