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

Abstract 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.