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Herein, we report a copper-catalyzed, atom-economical synthesis of 2,3-dihydro-4(1H)-pyrimidinones from alkynyl hydrazides. Control experiments suggest that the transformation proceeds via cyclization to form spirocyclic aminimides, followed by N\u2013N bond cleavage and intramolecular C\u2013H insertion.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c03996","type":"journal-article","created":{"date-parts":[[2026,10,5]],"date-time":"2026-10-05T08:02:10Z","timestamp":1791187330000},"page":"13098-13103","source":"Crossref","is-referenced-by-count":0,"title":["Synthesis of\n2,3-Dihydro-4(1\n                    <i>H<\/i>\n                    )-pyrimidinones\nthrough Copper-Catalyzed Skeletal Rearrangement of Spirocyclic Aminimides"],"prefix":"10.1021","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9324-3463","authenticated-orcid":true,"given":"Motohiro","family":"Yasui","sequence":"first","affiliation":[{"name":"Kyoto Institute of Technology , , Matsugasaki, Sakyo-ku , ,","place":["Kyoto, Japan, 606-8585"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Seinosuke","family":"Okumura","sequence":"additional","affiliation":[{"name":"Kyoto Institute of Technology , , Matsugasaki, Sakyo-ku , ,","place":["Kyoto, Japan, 606-8585"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shion","family":"Fujitomo","sequence":"additional","affiliation":[{"name":"Kobe Pharmaceutical University , Motoyamakita, Higashinada , ,","place":["Kobe, Japan, 658-8558"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nozomi","family":"Ogasawara","sequence":"additional","affiliation":[{"name":"Kobe Pharmaceutical University , Motoyamakita, Higashinada , ,","place":["Kobe, Japan, 658-8558"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1196-2737","authenticated-orcid":true,"given":"Takahiro","family":"Yamada","sequence":"additional","affiliation":[{"name":"Kobe Pharmaceutical University , Motoyamakita, Higashinada , ,","place":["Kobe, Japan, 658-8558"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2330-0201","authenticated-orcid":true,"given":"Norihiko","family":"Takeda","sequence":"additional","affiliation":[{"name":"Kobe Pharmaceutical University , Motoyamakita, Higashinada , ,","place":["Kobe, Japan, 658-8558"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8003-2971","authenticated-orcid":true,"given":"Masafumi","family":"Ueda","sequence":"additional","affiliation":[{"name":"Kobe Pharmaceutical University , Motoyamakita, Higashinada , ,","place":["Kobe, Japan, 658-8558"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,5]]},"reference":[{"key":"2026101608462745700_cit1a","doi-asserted-by":"publisher","first-page":"16278","DOI":"10.1021\/acsomega.1c05839","article-title":"Novel Dihydropyrimidinone Derivatives as Potential\nP-Glycoprotein Modulators","volume":"7","author":"Bijani","year":"2022","journal-title":"ACS Omega"},{"key":"2026101608462745700_cit1b","doi-asserted-by":"publisher","first-page":"7","DOI":"10.1016\/j.ejphar.2009.04.019","article-title":"aDP7, a Novel\nDihydropyridine Multidrug Resistance Reverter, Shows Only Weak Inhibitory\nActivity on Human CYP3A Enzyme(s)","volume":"614","author":"D\u2019Elia","year":"2009","journal-title":"Eur. 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Lett."},{"key":"2026101608462745700_cit1e","doi-asserted-by":"publisher","first-page":"11469","DOI":"10.1021\/acsomega.8b01987","article-title":"Asymmetric\nEntry into 10b-Aza-Analogues of Amaryllidaceae Alkaloids Reveals a\nPronounced Electronic Effect on Antiviral Activity","volume":"3","author":"Brown","year":"2018","journal-title":"ACS Omega"},{"key":"2026101608462745700_cit2a","doi-asserted-by":"publisher","first-page":"6393","DOI":"10.1002\/ejoc.201000852","article-title":"Functionalization of\n(2S)-Isopropyl-5-iodo-2,3-dihydro-4(H)-pyrimidin-4-ones\nby a Suzuki\u2013Miyaura Cross-Coupling Reaction Using Aryltrifluoroborate\nSalts: Convenient Enantioselective Preparation of \u03b1-Substituted\n\u03b2-Amino Acids","volume":"2010","author":"Stefani","year":"2010","journal-title":"Eur. J. Org. 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Commun."},{"key":"2026101608462745700_cit8a","doi-asserted-by":"publisher","first-page":"3930","DOI":"10.1021\/ol4016892","article-title":"Efficient Synthesis of Imino-Methano Tro\u0308ger\nBases by Nitrene Insertions into C\u2013N Bonds","volume":"15","author":"Pujari","year":"2013","journal-title":"Org. Lett."},{"key":"2026101608462745700_cit8b","doi-asserted-by":"publisher","first-page":"2451","DOI":"10.1039\/p19740002451","article-title":"Heterocyclic Syntheses. Part XXVIII. Ortho-Dialkylaminobenzenesulphonyl Azides, -Benzoyl Azides,\nand -Benzoyldiazomethanes","author":"Martin","year":"1974","journal-title":"J. Chem. Soc., Perkin\nTrans. 1"},{"key":"2026101608462745700_cit8c","doi-asserted-by":"publisher","first-page":"1319","DOI":"10.1039\/c29710001319","article-title":"The Decomposition\nof Ortho-Secondary Amino-Substituted Aryl-Sulphonyl\nAzides and Carbonyl Azides","author":"Martin","year":"1971","journal-title":"J. Chem. Soc. D"},{"key":"2026101608462745700_cit9a","doi-asserted-by":"publisher","first-page":"198","DOI":"10.1002\/cjoc.70365","article-title":"Skeleton Editing of\n2-Aryloxazines with CF3-Ynones Leading to Isoindolone-Fused\nCF3-Benzooxazocines Possessing Potent Anti-ZIKV and Anti-Cancer\nActivities","volume":"44","author":"Jiang","year":"2026","journal-title":"Chin. J. Chem."},{"key":"2026101608462745700_cit9b","doi-asserted-by":"publisher","first-page":"1366","DOI":"10.1002\/cjoc.70486","article-title":"Divergent Synthesis of CF3-Polycyclic Compounds with Potent Anticancer Activity via CHA-Initiated\nDouble or Triple Annulation of 3-Alkenyl-1,2,4-oxadiazolones with\nCF3-Ynones","volume":"44","author":"Li","year":"2026","journal-title":"Chin. J. Chem."},{"key":"2026101608462745700_cit10a","doi-asserted-by":"publisher","first-page":"5061","DOI":"10.1039\/b905820f","article-title":"Catalytic\nC\u2013H\nAmination: Recent Progress and Future Directions","author":"Collet","year":"2009","journal-title":"Chem. Commun."},{"key":"2026101608462745700_cit10b","doi-asserted-by":"publisher","first-page":"911","DOI":"10.1021\/ar200318q","article-title":"Metal-Catalyzed Nitrogen-Atom\nTransfer Methods for the Oxidation of Aliphatic C\u2013H Bonds","volume":"45","author":"Roizen","year":"2012","journal-title":"Acc. Chem. Res."},{"key":"2026101608462745700_cit10c","doi-asserted-by":"publisher","first-page":"9247","DOI":"10.1021\/acs.chemrev.6b00644","article-title":"Transition Metal-Catalyzed C\u2013H Amination: Scope,\nMechanism, and Applications","volume":"117","author":"Park","year":"2017","journal-title":"Chem. Rev."},{"key":"2026101608462745700_cit11","doi-asserted-by":"publisher","first-page":"558","DOI":"10.1016\/0378-5963(79)90047-3","article-title":"Oxidation\nof Copper in Controlled\nClean Air and Standard Laboratory Air at 50\u00b0C to 150 \u00b0C","volume":"2","author":"Pinnel","year":"1979","journal-title":"Appl. Surf. Sci."},{"key":"2026101608462745700_cit13","doi-asserted-by":"publisher","first-page":"1617","DOI":"10.1016\/0010-938X(92)90038-5","article-title":"An X-ray Photo-electron\nSpectroscopic Investigation of the Air-formed Film on Copper","volume":"33","author":"Chawla","year":"1992","journal-title":"Corros. Sci."}],"container-title":["Organic Letters"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.orglett.6c03996","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/orlef7\/article-pdf\/doi\/10.1021\/acs.orglett.6c03996\/68741932\/acs.orglett.6c03996.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/orlef7\/article-pdf\/doi\/10.1021\/acs.orglett.6c03996\/68741932\/acs.orglett.6c03996.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,16]],"date-time":"2026-10-16T13:04:21Z","timestamp":1792155861000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/orlef7\/article\/28\/41\/13098\/5444360\/Synthesis-of-2-3-Dihydro-4-1H-pyrimidinones"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,10,5]]},"references-count":33,"journal-issue":{"issue":"41","published-online":{"date-parts":[[2026,10,5]]},"published-print":{"date-parts":[[2026,10,16]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.orglett.6c03996","relation":{},"ISSN":["1523-7060","1523-7052"],"issn-type":[{"value":"1523-7060","type":"print"},{"value":"1523-7052","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,10,5]]}}}