Photocatalytic Enantioselective Hydrosulfonylation of α,β‐Unsaturated Carbonyls with Sulfonyl Chlorides

Abstract This research explores the enantioselective hydrosulfonylation of various α,β‐unsaturated carbonyl compounds via the use of visible light and redox‐active chiral Ni‐catalysis, facilitating the synthesis of enantioenriched α‐chiral sulfones with remarkable enantioselectivity (exceeding 99 % ee). A significant challenge entails enhancing the reactivity between chiral metal‐coordinated carbonyl compounds and moderate electrophilic sulfonyl radicals, aiming to minimize the background reactions. The success of our approach stems from two distinctive attributes: 1) the Cl‐atom abstraction employed for sulfonyl radical generation from sulfonyl chlorides, and 2) the single‐electron reduction to produce a key enolate radical Ni‐complex. The latter process appears to enhance the feasibility of the sulfonyl radical's addition to the electron‐rich enolate radical. An in‐depth investigation into the reaction mechanism, supported by both experimental observations and theoretical analysis, offers insight into the intricate reaction process. Moreover, the versatility of our methodology is highlighted through its successful application in the late‐stage functionalization of complex bioactive molecules, demonstrating its practicality as a strategy for producing α‐chiral sulfones.