Ni-Catalyzed Enantioselective Suzuki–Miyaura-Type Coupling of Styrene Oxides with Arylboronic Acids

Organoboron compounds are universally recognized as highly valuable synthetic building blocks, while the Suzuki–Miyaura cross-coupling has firmly established itself as a reliable platform for C–C bond formation. These salient features have fostered its widespread application across medicinal chemistry and materials science. Herein, a nickel-catalyzed, exogenous base-free, enantioselective Suzuki–Miyaura-type coupling of styrene oxides with arylboronic acids is reported. This reaction demonstrates high regioselectivity and enantioselectivity, a broad substrate scope, versatility for the late-stage modifications of bioactive molecules, and capability for synthesizing chiral drug precursors. Additionally, aryl aziridines can be employed as alternative coupling partners. Mechanistic studies confirm a stereoconvergent pathway involving radical intermediates, with in situ-generated alkoxide anions acting as the essential base. This methodology provides a practical approach for synthesizing enantioenriched diaryl alcohols and amines, which are valuable structural skeletons in pharmaceuticals and natural products.