Hui-Ling Ma, Xinhua Wang, S.G. Ma, Ming‐Hua Xu, Jun Zhang, Xiaoyu Zhou, Jie Wu
A copper-catalyzed sulfinylation of boronic acids with sulfinates was achieved to access a range of aryl/alkenyl sulfoxides. Dialkyl dicarbonates served as the key activator, effectively promoting the desired sulfinylation process and suppressing the undesired pathway to the thiosulfonate byproduct. Preliminary mechanistic studies indicated that this transformation favors a copper-mediated nucleophilic substitution over a Suzuki-type cross-coupling process. This protocol paves the way for the metal-catalyzed establishment of a C-S(=O) bond from readily available sulfinates.