{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,17]],"date-time":"2026-08-17T14:30:12Z","timestamp":1786977012816,"version":"build-2736575974"},"reference-count":89,"publisher":"Wiley","issue":"18","license":[{"start":{"date-parts":[[2023,1,25]],"date-time":"2023-01-25T00:00:00Z","timestamp":1674604800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100000057","name":"National Institute of General Medical Sciences","doi-asserted-by":"publisher","award":["R35-GM141558"],"award-info":[{"award-number":["R35-GM141558"]}],"id":[{"id":"10.13039\/100000057","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2023,4,24]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>A practical method for the efficient and enantioselective preparation of versatile ketones and aldehydes that contain an \u03b1\u2010quaternary stereocenter is described. Reactions utilize simple carboxylic acid or ester starting materials, a monodentate chiral phosphine, and afford a variety of aryl, alkenyl, alkynyl, and alkyl\u2010substituted ketone and aldehyde products in 25\u201394\u2009% yield and 90\u2009:\u200910 to &gt;99\u2009:\u20091 enantiomeric ratio. Reactions proceed by acyl substitution with in situ formed chiral allylic nucleophiles, and display selectivity and conversion dependence on a protic additive. The utility of the approach is demonstrated through several product transformations.<\/jats:p>","DOI":"10.1002\/anie.202215855","type":"journal-article","created":{"date-parts":[[2023,1,3]],"date-time":"2023-01-03T11:32:46Z","timestamp":1672745566000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["A Catalytic Method for the Enantioselective Synthesis of \u03b1\u2010Quaternary Ketones, \u03b1\u2010Ketoesters and Aldehydes"],"prefix":"10.1002","volume":"62","author":[{"given":"Emilie","family":"Wheatley","sequence":"first","affiliation":[{"name":"Department of Chemistry University of North Carolina at Chapel Hill  Chapel Hill NC 27599-3290 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Joseph M.","family":"Zanghi","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of North Carolina at Chapel Hill  Chapel Hill NC 27599-3290 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Miles M.","family":"Mason","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of North Carolina at Chapel Hill  Chapel Hill NC 27599-3290 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7537-9420","authenticated-orcid":false,"given":"Simon J.","family":"Meek","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of North Carolina at Chapel Hill  Chapel Hill NC 27599-3290 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,1,25]]},"reference":[{"key":"e_1_2_3_1_1","unstructured":"\u00a0"},{"key":"e_1_2_3_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19980302)37:4<388::AID-ANIE388>3.0.CO;2-V"},{"key":"e_1_2_3_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19980216)110:4<402::AID-ANGE402>3.0.CO;2-6"},{"key":"e_1_2_3_3_2","doi-asserted-by":"crossref","unstructured":"B. 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Jiang Synthesis 2006 369\u2013396;","DOI":"10.1055\/s-2006-926302"},{"key":"e_1_2_3_4_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature14007"},{"key":"e_1_2_3_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2016.09.002"},{"key":"e_1_2_3_6_1","unstructured":"For recent reviews see:"},{"key":"e_1_2_3_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar5004658"},{"key":"e_1_2_3_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b01886"},{"key":"e_1_2_3_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/open.202000175"},{"key":"e_1_2_3_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.0c01115"},{"key":"e_1_2_3_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201703079"},{"key":"e_1_2_3_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201703079"},{"key":"e_1_2_3_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b04551"},{"key":"e_1_2_3_13_1","unstructured":"For catalytic enantioselective methods that generate acyclic ketones bearing \u03b1-tertiary stereocenters 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phthalimide-derived examples) were also found to be ineffective delivering little to no (<10\u2009% conv) product."},{"key":"e_1_2_3_68_1","unstructured":"Ethyl chloroformate derived acyl carbonates are slightly more stable but result in lower er (e.g. 8is formed in 92\u2009% NMR yield and 92\u2009:\u20098 er)."},{"key":"e_1_2_3_69_1","unstructured":"In cases of low conversion reactions lead to either returned allyldiboron or the corresponding deboroylated allyl boronate ester."},{"key":"e_1_2_3_70_1","unstructured":"For representative catalytic enantioselective examples 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