{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,20]],"date-time":"2026-10-20T12:05:34Z","timestamp":1792497934703,"version":"4.5.0"},"reference-count":63,"publisher":"Wiley","issue":"6","license":[{"start":{"date-parts":[[2024,1,8]],"date-time":"2024-01-08T00:00:00Z","timestamp":1704672000000},"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":["GM125206"],"award-info":[{"award-number":["GM125206"]}],"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":[[2024,2,5]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    A method for the generation of tertiary carbanions via a deaminative radical\u2010polar crossover is reported using redox active imines from \u03b1\u2010tertiary primary amines. A variety of benzylic amines and amino esters can be used in this approach, with the latter engaging in a novel \u201caza\u2010Reformatsky\u201d reaction. Electronic trends correlate the stability of the resulting carbanion with reaction efficiency. The anions can be trapped with different electrophiles including aldehydes, ketones, imines, Michael acceptors, and H\n                    <jats:sub>2<\/jats:sub>\n                    O\/D\n                    <jats:sub>2<\/jats:sub>\n                    O. Selective anion formation can be achieved in the presence of another equivalent or more acidic C\u2212H bond in both an inter\u2010 and intramolecular fashion. Mechanistic studies suggest the intermediacy of a discrete carbanion intermediate.\n                  <\/jats:p>","DOI":"10.1002\/anie.202317563","type":"journal-article","created":{"date-parts":[[2024,1,8]],"date-time":"2024-01-08T09:32:31Z","timestamp":1704706351000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":30,"title":["Photoredox\u2010Catalyzed Generation of Tertiary Anions from Primary Amines via a Radical Polar Crossover"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3090-2748","authenticated-orcid":false,"given":"Austin D.","family":"Marchese","sequence":"first","affiliation":[{"name":"Department of Chemistry Columbia University  New York NY 10027 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0675-5928","authenticated-orcid":false,"given":"Julia R.","family":"Dorsheimer","sequence":"additional","affiliation":[{"name":"Department of Chemistry Columbia University  New York NY 10027 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6287-8669","authenticated-orcid":false,"given":"Tomislav","family":"Rovis","sequence":"additional","affiliation":[{"name":"Department of Chemistry Columbia University  New York NY 10027 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,1,8]]},"reference":[{"key":"e_1_2_3_1_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.abn8382"},{"key":"e_1_2_3_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5NP00096C"},{"key":"e_1_2_3_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jcim.1c00811"},{"key":"e_1_2_3_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00386"},{"key":"e_1_2_3_5_1","first-page":"68","volume":"6","author":"Jin Y.","year":"2017","journal-title":"J. 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Deprotonation occurs competitively at this position generating an unproductive aza-allyl radical. See: M.\u2005A. Ashley Photoredox-Catalyzed Site-Selective Functionalization of Primary Amine Derivatives Doctoral dissertation Columbia University 2020."},{"key":"e_1_2_3_55_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2004.07.018"},{"key":"e_1_2_3_56_1","first-page":"79","volume":"47","author":"Sailer M.","year":"2015","journal-title":"Synthesis"},{"key":"e_1_2_3_57_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo060316a"},{"key":"e_1_2_3_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b08933"},{"key":"e_1_2_3_59_1","unstructured":"\u00a0"},{"key":"e_1_2_3_60_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201601478"},{"key":"e_1_2_3_61_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.electacta.2010.02.099"},{"key":"e_1_2_3_62_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.2c03600"},{"key":"e_1_2_3_63_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja4100595"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202317563","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,7,18]],"date-time":"2024-07-18T08:12:51Z","timestamp":1721290371000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202317563"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,1,8]]},"references-count":63,"journal-issue":{"issue":"6","published-print":{"date-parts":[[2024,2,5]]}},"alternative-id":["10.1002\/anie.202317563"],"URL":"https:\/\/doi.org\/10.1002\/anie.202317563","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,1,8]]},"assertion":[{"value":"2023-11-17","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2024-01-08","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202317563"}}