Dual Nickel/Photoredox-Catalyzed Regio- and Enantioselective Alkenylation of Epoxides.

β-Chiral phenethyl alcohols represent a privileged scaffold in bioactive molecules, chemical probes, and functional materials, serving as versatile synthons in organic synthesis. Herein, we report the first Ni/photoredox-catalyzed stereoconvergent C(sp3)-C(sp2) cross-electrophile coupling of racemic epoxides with alkenyl bromides, delivering β-alkenyl phenylethanol with high enantioselectivity (up to 95% ee), excellent E-stereoselectivity, and complete regiocontrol. The enantioenriched products serve as versatile intermediates for diverse chiral synthons, enabling further applications. Mechanistic studies suggest a stereoconvergent pathway involving regioselective halide ring-opening of epoxides, followed by enantioselective coupling of the generated β-hydroxy benzyl halides with alkenyl bromides.