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Herein, a novel family of PNP ligands (<jats:bold>W\u2010Phos<\/jats:bold>) was designed and applied in copper\u2010catalyzed asymmetric addition of linear Grignard reagents to aryl alkyl ketones, allowing facile access to versatile chiral tertiary alcohols in good to high yields with excellent enantioselectivities (up to 94\u2009% yield, 96\u2009% ee). The process can also be used to synthesize chiral allylic tertiary alcohols from more challenging \u03b1,\u03b2\u2010unsaturated ketones. Notably, the potential utility of this method is demonstrated in the gram\u2010scale synthesis and modification of various densely functionalized medicinally relevant molecules.<\/jats:p>","DOI":"10.1002\/anie.202204443","type":"journal-article","created":{"date-parts":[[2022,5,12]],"date-time":"2022-05-12T14:39:16Z","timestamp":1652366356000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":30,"title":["Synthesis of W\u2010Phos Ligand and Its Application in the Copper\u2010Catalyzed Enantioselective Addition of Linear Grignard Reagents to Ketones"],"prefix":"10.1002","volume":"61","author":[{"given":"Wenjun","family":"Luo","sequence":"first","affiliation":[{"name":"Department of Chemistry Fudan University 2005 Songhu Road Shanghai 200438 P. R. China"},{"name":"Zhuhai Fudan Innovation Institute Hengqin NewArea, Zhuhai 519000 P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Li\u2010Ming","family":"Zhang","sequence":"additional","affiliation":[{"name":"Department of Chemistry Fudan University 2005 Songhu Road Shanghai 200438 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhan\u2010Ming","family":"Zhang","sequence":"additional","affiliation":[{"name":"Department of Chemistry Fudan University 2005 Songhu Road Shanghai 200438 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4636-2846","authenticated-orcid":false,"given":"Junliang","family":"Zhang","sequence":"additional","affiliation":[{"name":"Department of Chemistry Fudan University 2005 Songhu Road Shanghai 200438 P. R. China"},{"name":"Zhuhai Fudan Innovation Institute Hengqin NewArea, Zhuhai 519000 P.R. China"},{"name":"State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry, CAS P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,5,31]]},"reference":[{"key":"e_1_2_3_1_1","unstructured":"For books see:"},{"key":"e_1_2_3_2_2","first-page":"1","volume-title":"Quaternary stereocenters, challenges and solutions for organic synthesis","author":"Arimoto H.","year":"2005"},{"key":"e_1_2_3_3_2","doi-asserted-by":"crossref","first-page":"25","DOI":"10.1002\/3527606858.ch2","volume-title":"Quaternary stereocenters, challenges and solutions for organic synthesis","author":"Vries J. 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derivatives developed by us are commercially available from Daicel and Strem and are also easily prepared in 2\u20134 steps from chiraltert-butane sulfinamide (TBSA)."},{"key":"e_1_2_3_93_1","unstructured":"For Ming-Phos ligands see:"},{"key":"e_1_2_3_94_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201401067"},{"key":"e_1_2_3_94_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201401067"},{"key":"e_1_2_3_95_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201913367"},{"key":"e_1_2_3_95_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201913367"},{"key":"e_1_2_3_96_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c02876"},{"key":"e_1_2_3_97_1","unstructured":"For Xu-Phos ligands see:"},{"key":"e_1_2_3_98_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201806372"},{"key":"e_1_2_3_98_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201806372"},{"key":"e_1_2_3_99_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b10883"},{"key":"e_1_2_3_100_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.gresc.2021.05.004"},{"key":"e_1_2_3_101_1","unstructured":"For PC-Phos ligands see:"},{"key":"e_1_2_3_102_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b00178"},{"key":"e_1_2_3_103_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201904805"},{"key":"e_1_2_3_103_3","doi-asserted-by":"crossref","first-page":"11566","DOI":"10.1002\/ange.201904805","volume":"131","year":"2019","journal-title":"Angew. Chem."},{"key":"e_1_2_3_104_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202010164"},{"key":"e_1_2_3_104_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202010164"},{"key":"e_1_2_3_105_1","unstructured":"For Xiang-Phos ligands see:"},{"key":"e_1_2_3_106_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201912408"},{"key":"e_1_2_3_106_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201912408"},{"key":"e_1_2_3_107_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0CC04996D"},{"key":"e_1_2_3_108_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC01391A"},{"key":"e_1_2_3_109_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b11938"},{"key":"e_1_2_3_110_1","unstructured":"For WJ-Phos ligands see:"},{"key":"e_1_2_3_111_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b02080"},{"key":"e_1_2_3_112_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b04354"},{"key":"e_1_2_3_113_1","unstructured":"Deposition Number2111834 (forW15)contains the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."},{"key":"e_1_2_3_114_1","unstructured":"\u00a0"},{"key":"e_1_2_3_115_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja046632t"},{"key":"e_1_2_3_116_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0585634"},{"key":"e_1_2_3_117_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr068424k"},{"key":"e_1_2_3_118_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aaf1983"},{"key":"e_1_2_3_119_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b07344"},{"key":"e_1_2_3_120_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201906237"},{"key":"e_1_2_3_120_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201906237"},{"key":"e_1_2_3_121_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-019-11345-z"},{"key":"e_1_2_3_122_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.1c01544"},{"key":"e_1_2_3_123_1","unstructured":"\u00a0"},{"key":"e_1_2_3_124_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b08075"},{"key":"e_1_2_3_125_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c03898"},{"key":"e_1_2_3_126_2","unstructured":"J. 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