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Conventional approaches typically rely on precious metal catalysts. Herein, we report the first nickel\u2010catalyzed asymmetric hydrogenation of all\u2010carbon tetrasubstituted electron\u2010deficient alkenes. The developed catalytic system exhibits a broad substrate scope, delivering excellent reactivity and enantioselectivity across 37 examples (up to 99% yield, &gt;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.<\/jats:p>","DOI":"10.1002\/anie.202523659","type":"journal-article","created":{"date-parts":[[2026,1,5]],"date-time":"2026-01-05T06:02:41Z","timestamp":1767592961000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Nickel\u2010Catalyzed Asymmetric Hydrogenation of All\u2010Carbon Tetrasubstituted Alkenes Enabled by van der Waals Interactions"],"prefix":"10.1002","volume":"65","author":[{"given":"Congcong","family":"Yin","sequence":"first","affiliation":[{"name":"Hubei Key Laboratory of Natural Products Research and Development College of Biological and Pharmaceutical Sciences China Three Gorges University  Yichang 443002 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zichang","family":"Wang","sequence":"additional","affiliation":[{"name":"Hubei Key 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