Photogeneration of β-Borylsilyl Radical via Decarboxylation of -Hydroxyphthalimide Esters.

-borylsilylalkanes are versatile intermediates in organic synthesis, and the traditional synthesis methods have mainly focused on metal reagents, the insertion reactions of diazo compounds, and hydrosilylation/hydroborylation reactions of unsaturated bonds. Herein, a novel, efficient -borylsilylalkanes synthesis via a radical approach is reported. This method introduced a β--borylsilyl NHPI ester as the precursor of the β-borylsilyl radical that, coupling with radical acceptors under photo conditions, and the corresponding -borylsilylalkanes bearing unsaturated bonds, facilitate subsequent transformations.

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.