Rapid Synthesis of β‑Chiral Sulfones by Ni-Organophotocatalyzed Enantioselective Sulfonylalkenylation of Alkenes

β-Chiral sulfones are substructures widespread in drug molecules and bioactive targets and serve as important chiral synthons in organic synthesis yet are challenging to access. Herein, a three-component strategy enabled by visible-light- and Ni-catalyzed sulfonylalkenylation of styrenes for the synthesis of enantioenriched β-chiral sulfones has been developed. This dual-catalysis strategy allows for one-step skeletal assembly along with the control of enantioselectivity in the presence of a chiral ligand, providing an efficient and straightforward access to enantioenriched β-alkenyl sulfones from easily available and simple starting materials. Mechanistic investigations reveal that the reaction undergoes a chemoselective radical addition over two alkenes followed by a Ni-intercepted asymmetric Csp3–Csp2 coupling with alkenyl halides.