Ni-Catalyzed Hydrosulfonylation of Alkenes with Aromatic Iodides and K 2 S 2 O 5 .

Hydrosulfonylation of alkenes with readily available aromatic iodides via a SO 2 -insetion strategy is presented. The combination of non-noble Ni catalysis with ( i Pr) 3 SiH as the final reductant enables the efficient formation of aryl and heteroaryl sulfinate intermediates, which undergo Michael-type additions to electron-deficient alkenes for initiating the hydrosulfonylation process. Moreover, the superiority of this protocol is demonstrated by broad substrate scope and good functional group compatibility.