Photo-induced decarboxylative C-S bond formation to access sterically hindered unsymmetric S-alkyl thiosulfonates and SS-alkyl thiosulfonates

Due to the high reactivity and versatility of benzenesulfonothioates, significant advancements have been made in constructing C-S bonds. However, there are certain limitations in the synthesis of S-thiosulfonates and SS-thiosulfonates, especially when dealing with substantial steric hindrance, which poses a significant challenge. Herein, we present an innovative approach for assembling unsymmetric S-thiosulfonates and unsymmetric SS-thiosulfonates through the integration of dual copper/photoredox catalysis. Moreover, we also realized the one-pot strategy by directly using carboxylic acids as raw materials by in-situ activation of them to access S-thiosulfonates and SS-thiosulfonates without further purification and presynthesis of NHPI esters. The envisaged synthesis and utilization of these reagents are poised to pioneer an innovative pathway for fabricating a versatile spectrum of mono-, di-, and polysulfide compounds. Furthermore, they introduce a class of potent sulfenylating reagents, empowering the synthesis of intricate unsymmetrical disulfides that were previously challenging to access. The conventional method for synthesizing thioether compounds typically relies on thiol, disulfide, and sulfinyl halide as initial substances, suffering from strong odors, limited availability, and reactivity issues. Here, the authors present an approach for assembling S-thiosulfonates and SS-thiosulfonates through the integration of dual copper/photoredox catalysis