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This redox\u2010neutral cascade simultaneously forges C\u2500C and C\u2500P bonds, providing direct access to valuable 3,3\u2010disubstituted phosphorylated oxindoles with quaternary stereocenters in good yields and high ee values. Notably, the reaction exhibits a unique substrate\u2010controlled enantiodivergence: simply changing the leaving group (I vs. OTf) on the alkene partner switches the configuration of the product while employing the same enantiomer of the chiral catalyst. The synthetic utility is further demonstrated through product derivatizations. Density functional theory (DFT) calculations reveal that the leaving group dictates the order of migratory insertion versus anion exchange and, crucially, inverts the chiral environment at the enantioselectivity\u2010determining oxidative addition transition state, providing a clear rationale for the observed stereodivergence.<\/jats:p>","DOI":"10.1002\/anie.4623924","type":"journal-article","created":{"date-parts":[[2026,6,7]],"date-time":"2026-06-07T16:37:52Z","timestamp":1780850272000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Substrate\u2010Controlled Enantiodivergence in Ni\u2010Catalyzed Access to Phosphorylated Oxindoles With Quaternary Stereocenters"],"prefix":"10.1002","volume":"65","author":[{"given":"Haimeng","family":"Zhu","sequence":"first","affiliation":[{"name":"Department of Chemistry Hong Kong Baptist University  Hong Kong 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