C(sp 2 )‐Arylsulfones Directly from Arylsulfonyl Chlorides with Boronic Acids by Photoactivation of Boosted EDA Complexes

Abstract Directly with arylsulfonyl chlorides, a green and efficient deborylativesulfonylation of aryl(alkenyl)boronic acids has been developed to access both diarylsulfones and vinylarylsulfones in moderate to excellent yields at room temperature under visible‐light irradiation. This protocol features broad C(sp 2 )‐arylsulfone applicability, simple operation, accessibility of raw materials and ease of scale‐up. The key to the success of this photoredox transformation is introducing catalytic amounts of additives, naphthalen‐2‐ols, thus boosting the formed electron donor‐acceptor (EDA) complexes, which can dramatically improve not only the reaction efficiency but also the selectivity. This strategy was inspired and derived from specific substrates, representing a rare paradigm of how to exploit a more general reaction system. Moreover, extensive control experiments provide insights into the proposed mechanism.