Stereoinvertive Cross-Coupling for Trisubstituted Alkenes Enabled by the Sulfoximine Leaving Group

Although stereodivergent synthesis of alkenes is highly valuable in organic synthesis, its scope has been largely confined to disubstituted alkenes, and extension to multisubstituted alkenes remains a formidable challenge. Herein, we report a stereoinvertive cross-coupling enabled by alkenyl sulfoximines with aryl boronic acid in the presence of nickel catalysis, in stark contrast to typical cross-coupling reactions of alkenyl (pseudo)halides, which proceed with retention of stereochemistry of substrates. Given that our previously developed Pd-catalyzed Suzuki–Miyaura cross-coupling of alkenyl sulfoximines proceeds in a stereoretentive fashion, this Ni-catalyzed protocol paves the way for the stereodivergent synthesis of trisubstituted alkenes from a common precursor. Combined experimental and computational studies reveal that the sulfoximine group plays a pivotal role in achieving the stereoinvertive transformation with its coordinating ability.