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However, the use of asymmetric multi\u2010component reactions that build two C\u2212C bonds on the same carbonic center with concomitant assembly of quaternary stereocenters is rare and remains challenging. Herein, we disclose an enantioselective three\u2010component reaction of \u03b1\u2010diazo ketones with alkenes and 1,3,5\u2010triazines under dirhodium\/chiral phosphoric acid cooperative catalysis, which leads to a practical and atom\u2010economic synthesis of poly\u2010functionalized chiral ketones that bear a \u03b1\u2010quaternary stereocenter in generally good to high yields with excellent enantioselectivities. In comparison to the previous method for the construction of tertiary and quaternary stereocenters via carbene <jats:italic>gem<\/jats:italic>\u2010difunctionalization reactions, this reaction features an unprecedented <jats:italic>gem<\/jats:italic>\u2010dialkylation process via sequential installation of two C\u2212C bonds on the carbene center in one reaction, providing an essential complement to the asymmetric construction of all\u2010carbon quaternary stereocenters using common and readily available starting materials.<\/jats:p>","DOI":"10.1002\/anie.202302371","type":"journal-article","created":{"date-parts":[[2023,5,2]],"date-time":"2023-05-02T10:10:21Z","timestamp":1683022221000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":28,"title":["Construction of Chiral Quaternary Carbon Centers via Asymmetric Metal Carbene <i>gem<\/i>\u2010Dialkylation"],"prefix":"10.1002","volume":"62","author":[{"given":"Shanliang","family":"Dong","sequence":"first","affiliation":[{"name":"School of Pharmaceutical Sciences Sun Yat-sen University  510006 Guangzhou P.\u2005R. 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