{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,2]],"date-time":"2026-08-02T07:00:14Z","timestamp":1785654014892,"version":"3.56.0"},"reference-count":62,"publisher":"Wiley","license":[{"start":{"date-parts":[[2024,9,12]],"date-time":"2024-09-12T00:00:00Z","timestamp":1726099200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Transformations enabling the synthesis of \u03b1\u2010alkyl, \u03b1\u2032\u20102\u2010azinyl amines by addition of 2\u2010heteroaryl\u2010based nucleophiles to in situ<jats:italic>\u2010<\/jats:italic>generated and non\u2010activated alkyl\u2010substituted iminium ions are extremely rare. Approaches involving classical 2\u2010azinyl organometallics, such as the corresponding Grignard reagents, often fail to produce the desired products. Here, we report an operationally straightforward solution to this problem through the development of a multicomponent coupling process wherein a soft 2\u2010azinyl indium nucleophile, generated in situ from the corresponding 2\u2010iodo heteroarene and indium powder, adds to an iminium ion that is also formed directly in the reaction. This modular carbonyl azinylative amination (CAzA) displays a broad scope and only a metal reductant is needed to generate a reactive 2\u2010azinyl nucleophile. Beyond the addition to iminium ions, the 2\u2010azinyl addition to polyfluoromethyl ketones forms the corresponding tertiary alcohols. Together, the products of these reactions possess a high degree of functionality, are typically challenging to synthesize by other methods, and contain motifs recognized as privileged in the context of pharmaceuticals and agrochemicals.<\/jats:p>","DOI":"10.1002\/anie.202408287","type":"journal-article","created":{"date-parts":[[2024,7,12]],"date-time":"2024-07-12T09:37:30Z","timestamp":1720777050000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Modular Synthesis of Heterobenzylic Amines via Carbonyl Azinylative Amination"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5311-2290","authenticated-orcid":false,"given":"Alex A.","family":"Rafaniello","sequence":"first","affiliation":[{"name":"Yusuf Hamied Department of Chemistry University of Cambridge  Lensfield Rd Cambridge CB2 1EW United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5454-0537","authenticated-orcid":false,"given":"Roopender","family":"Kumar","sequence":"additional","affiliation":[{"name":"Yusuf Hamied Department of Chemistry University of Cambridge  Lensfield Rd Cambridge CB2 1EW United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rachel C.","family":"Phillips","sequence":"additional","affiliation":[{"name":"Yusuf Hamied Department of Chemistry University of Cambridge  Lensfield Rd Cambridge CB2 1EW United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7214-608X","authenticated-orcid":false,"given":"Matthew J.","family":"Gaunt","sequence":"additional","affiliation":[{"name":"Yusuf Hamied Department of Chemistry University of Cambridge  Lensfield Rd Cambridge CB2 1EW United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,9,12]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/jm501100b"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.2147\/DDDT.S329547"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/jm300801u"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/jm400186h"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/jm070027u"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/op0601013"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr940474e"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(99)00451-2"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6CC09172E"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201505167"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.6b00722"},{"key":"e_1_2_8_12_1","author":"Turro R. 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