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Herein, we report a new strategy that adopts the pyridinyl moiety as the coordinating group in the cobalt\u2010catalysed asymmetric nucleophilic addition\/alkylation of secondary phosphine oxides. A series of tertiary phosphine oxides were generated with up to 99\u2009% yield and 99.5\u2009%\n                    <jats:italic>ee<\/jats:italic>\n                    , and with broad functional\u2010group tolerance. Mechanistic studies reveal that (\n                    <jats:italic>R<\/jats:italic>\n                    )\u2010secondary phosphine oxides preferentially interact with the cobalt catalysts to produce P\u2010stereogenic compounds.\n                  <\/jats:p>","DOI":"10.1002\/anie.202111137","type":"journal-article","created":{"date-parts":[[2021,11,5]],"date-time":"2021-11-05T09:29:56Z","timestamp":1636104596000},"page":"27241-27246","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":115,"title":["Cobalt\u2010Catalysed Asymmetric Addition and Alkylation of Secondary Phosphine Oxides for the Synthesis of\n                    <i>P<\/i>\n                    \u2010Stereogenic Compounds"],"prefix":"10.1002","volume":"60","author":[{"given":"Zeng\u2010Hua","family":"Wu","sequence":"first","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shaanxi Normal University  620 Xi Changan Street Xi'an 710119 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"An\u2010Qi","family":"Cheng","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shaanxi Normal University  620 Xi Changan Street Xi'an 710119 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Meng","family":"Yuan","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shaanxi Normal University  620 Xi Changan Street Xi'an 710119 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ya\u2010Xuan","family":"Zhao","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shaanxi Normal University  620 Xi Changan Street Xi'an 710119 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huai\u2010Lan","family":"Yang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shaanxi Normal University  620 Xi Changan Street Xi'an 710119 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Li\u2010Hua","family":"Wei","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shaanxi Normal University  620 Xi Changan Street Xi'an 710119 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huai\u2010Yu","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shaanxi Normal University  620 Xi Changan Street Xi'an 710119 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tao","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shaanxi Normal University  620 Xi Changan Street Xi'an 710119 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zunting","family":"Zhang","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shaanxi Normal University  620 Xi Changan Street Xi'an 710119 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2791-1931","authenticated-orcid":false,"given":"Wei\u2010Liang","family":"Duan","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering Shaanxi Normal University  620 Xi Changan Street Xi'an 710119 China"},{"name":"College of Chemistry and Chemical Engineering Yangzhou University  180 Siwangting Road Yangzhou 225002 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2021,11,22]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020049i"},{"key":"e_1_2_2_3_2","volume-title":"Phosphorus Ligands in Asymmetric Catalysis: Synthesis and Applications, Vols.\u20051\u20133","author":"B\u00f6rner A.","year":"2008"},{"key":"e_1_2_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100244e"},{"key":"e_1_2_2_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527635207"},{"key":"e_1_2_2_6_2","doi-asserted-by":"crossref","first-page":"167","DOI":"10.1016\/B978-0-08-095167-6.00110-5","volume-title":"Comprehensive Chirality, Vol.\u20051","author":"Busacca C. 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