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The new method was easily scalable with low loadings of cobalt catalysts, and its synthetic utility was demonstrated in concise synthesis of chiral carbinols that are key motifs of drugs or synthetic precursors. The cobalt catalyst also provided high diastereoselectivity in the addition of chiral amino aldehydes. Mechanistic studies suggest cationic complexes of aryl\u2010cobalt(II) act as active species for asymmetric insertion. Lewis acidic titanium alkoxides assist ionization of aryl\u2010cobalt halides to form cationic complexes. The lowest\u2010energy transition states for insertion are stabilized by \u03c0\u2013\u03c0 stacking between the migrating aryl ring and\n                    <jats:italic>P<\/jats:italic>\n                    \u2010phenyl ring of Josiphos.\n                  <\/jats:p>","DOI":"10.1002\/anie.1980531","type":"journal-article","created":{"date-parts":[[2026,9,4]],"date-time":"2026-09-04T09:01:07Z","timestamp":1788512467000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Catalytic Enantioselective Addition of Aryl, Heteroaryl, and Alkenyl Halides to Aliphatic Aldehydes"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2222-6265","authenticated-orcid":false,"given":"Lantian","family":"Sun","sequence":"first","affiliation":[{"name":"State Key Laboratory of Chemical Oncogenomics Shenzhen Key Laboratory of Chemical Genomics School of Chemical Biology and Biotechnology Peking University 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