Nickel‐Catalyzed Asymmetric Hydrogenation of All‐Carbon Tetrasubstituted Alkenes Enabled by van der Waals Interactions

The asymmetric hydrogenation of all-carbon tetrasubstituted alkenes has long posed a significant challenge due to their pronounced steric hindrance. Conventional approaches typically rely on precious metal catalysts. Herein, we report the first nickel-catalyzed asymmetric hydrogenation of all-carbon tetrasubstituted electron-deficient alkenes. The developed catalytic system exhibits a broad substrate scope, delivering excellent reactivity and enantioselectivity across 37 examples (up to 99% yield, >99% ee, and TON up to 500). Combined experimental and computational studies reveal that van der Waals interactions play a pivotal role in governing enantioselectivity. This strategy further enables concise asymmetric syntheses of pharmaceutically relevant compounds, including Valerate and Esfenvalerate.