biostudies-literatureGuo YNational Natural Science Foundation of ChinaNational Natural Science Foundation of China (National Science Foundation of China)7313https://www.ebi.ac.uk/biostudies/studies/S-EPMC11344762biostudies-literatureUnknown15(1)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 theNature communicationsPhoto-induced decarboxylative C-S bond formation to access sterically hindered unsymmetric S-alkyl thiosulfonates and SS-alkyl thiosulfonates.PMC1134476221931013 and 22271105Guo YSong QLin GZhang MXu JfalsePhoto-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 the2024-01-01T00:00:00Z2024 Aug2025-04-18T16:54:11.392Z2025-04-07T04:21:46.826ZS-EPMC113447623918187510.1038/s41467-024-51334-5