{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T00:39:19Z","timestamp":1760315959674,"version":"build-2065373602"},"reference-count":51,"publisher":"Wiley","issue":"5","license":[{"start":{"date-parts":[[2023,11,29]],"date-time":"2023-11-29T00:00:00Z","timestamp":1701216000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001691","name":"Japan Society for the Promotion of Science","doi-asserted-by":"publisher","award":["project number 1088204"],"award-info":[{"award-number":["project number 1088204"]}],"id":[{"id":"10.13039\/501100001691","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2024,1,22]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Here we show that the <jats:italic>sp<\/jats:italic>\u2010hybridized nitrogen cation is strongly stabilized by a <jats:italic>peri<\/jats:italic>\u2010iodine substituent in the tetralone system. The cation is captured by anionic species such as CF<jats:sub>3<\/jats:sub>CO<jats:sub>2<\/jats:sub><jats:sup>\u2212<\/jats:sup>, affording hypervalent iodine(III) compounds with a short nitrogen\u2010iodine (N\u2212I) bond, in which the cation serves as a Lewis acid. Notably, the O\u2212I bond of the <jats:italic>O<\/jats:italic>\u2010trifluoroacetate or <jats:italic>O<\/jats:italic>\u2010acetate is intrinsically weaker than the N\u2212I bond due to its more ionic character and is further weakened by protonation in trifluoroacetic acid. As a result, the oxygen ligand can dissociate in the presence of a Br\u00f8nsted acid, affording a I<jats:sup>+<\/jats:sup> cation intermediate that retains the N\u2212I bond. We isolated the cation as the tetrafluoroborate, and characterized it experimentally by <jats:sup>1<\/jats:sup>H NMR spectroscopy and X\u2010ray structure analysis, and theoretically by means of DFT calculation. The results suggest that the N\u2212I bonded cation is intrinsically stable, and is weakly coordinated with water and the BF<jats:sub>4<\/jats:sub> counter anion or trifluoroacetate anion. This cation can be employed as a reagent for \u03b1\u2010oxidation of ketones.<\/jats:p>","DOI":"10.1002\/chem.202303393","type":"journal-article","created":{"date-parts":[[2023,11,21]],"date-time":"2023-11-21T06:54:21Z","timestamp":1700549661000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Stabilization of <i>sp<\/i>\u2010Hybridized Nitrogen Cation by Lewis Acid\u2010Base Complex Formation with Intramolecular Iodine"],"prefix":"10.1002","volume":"30","author":[{"given":"Tomohiro","family":"Fujino","sequence":"first","affiliation":[{"name":"Department of Organic and Medicinal Chemistry Graduate School of Pharmaceutical Sciences The University of Tokyo  7-3-1 Hongo Bunkyo-ku Tokyo 113-0033 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5099-9738","authenticated-orcid":false,"given":"Tadashi","family":"Hyodo","sequence":"additional","affiliation":[{"name":"Faculty of Pharmaceutical Sciences at Kagawa Campus Tokushima Bunri University  1314-1 Shido Sanuki Kagawa 769-2193 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8104-283X","authenticated-orcid":false,"given":"Yuko","family":"Otani","sequence":"additional","affiliation":[{"name":"Department of Organic and Medicinal Chemistry Graduate School of Pharmaceutical Sciences The University of Tokyo  7-3-1 Hongo Bunkyo-ku Tokyo 113-0033 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2629-716X","authenticated-orcid":false,"given":"Kentaro","family":"Yamaguchi","sequence":"additional","affiliation":[{"name":"Faculty of Pharmaceutical Sciences at Kagawa Campus Tokushima Bunri University  1314-1 Shido Sanuki Kagawa 769-2193 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5390-0203","authenticated-orcid":false,"given":"Tomohiko","family":"Ohwada","sequence":"additional","affiliation":[{"name":"Department of Organic and Medicinal Chemistry Graduate School of Pharmaceutical Sciences The University of Tokyo  7-3-1 Hongo Bunkyo-ku Tokyo 113-0033 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,11,29]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b12360"},{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202008798"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4684-0826-3"},{"key":"e_1_2_9_4_1","first-page":"167","volume":"42","author":"Ma S.","year":"2019","journal-title":"Acc. 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