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The development of readily accessible aldehydes as oxycarbene precursors is of significant research value, yet it has never been achieved before. Compounds with a better decomposable trifluoromethoxy (\u2212OCF3) group have found diverse applications in pharmaceutical and agricultural research and are considered promising PFAS\u2019s alternatives. Here, we report that (hetero)aryl-, alkenyl-, and alkynyl-aldehydes are readily converted (via isolable or in situ-utilized \u03b1-OCF3 secondary chlorides derived from O-trifluoromethylation\/chlorination of aldehydes) to unprecedented, structurally diverse free \u03b1-OCF3 carbenes to facilitate three reaction classes, including cyclopropanation, Si\u2013H insertion, and phosphonylation via phosphorus ylide. This approach opens avenues to access previously elusive but potentially valuable OCF3-containing compounds, including OCF3-substituted cyclopropanes, silanes, and phosphonates, expanding both organofluorine and carbene chemistry.<\/jats:p>","DOI":"10.1021\/jacs.6c10096","type":"journal-article","created":{"date-parts":[[2026,8,17]],"date-time":"2026-08-17T14:01:57Z","timestamp":1786975317000},"page":"38080-38091","source":"Crossref","is-referenced-by-count":0,"title":["Unlocking Free \u03b1-Trifluoromethoxy\nCarbene\nReactivity from Aldehyde"],"prefix":"10.1021","volume":"148","author":[{"given":"Hongye","family":"Zhu","sequence":"first","affiliation":[{"name":"Northeast Normal University , , ,","place":["Changchun, China, 130024"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chenxi","family":"Liu","sequence":"additional","affiliation":[{"name":"Northeast Normal University , , ,","place":["Changchun, China, 130024"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9817-7186","authenticated-orcid":true,"given":"Cong","family":"Xu","sequence":"additional","affiliation":[{"name":"Northeast Normal University , , ,","place":["Changchun, China, 130024"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8006-4626","authenticated-orcid":true,"given":"Mang","family":"Wang","sequence":"additional","affiliation":[{"name":"Northeast Normal University , , ,","place":["Changchun, China, 130024"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,17]]},"reference":[{"key":"2026090910084182500_cit1a","doi-asserted-by":"publisher","first-page":"5822","DOI":"10.1021\/acs.jmedchem.7b01788","article-title":"Fluorine and Fluorinated Motifs in the Design and Application\nof Bioisosteres for Drug Design","volume":"61","author":"Meanwell","year":"2018","journal-title":"J. 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Lett."},{"key":"2026090910084182500_cit37","doi-asserted-by":"publisher","first-page":"11986","DOI":"10.1002\/anie.201706868","article-title":"Enantioselective\nConstruction of\nTrifluoromethoxylated Stereogenic Centers by a Nickel-Catalyzed Asymmetric\nSuzuki\u2013Miyaura Coupling of Secondary Benzyl Bromides","volume":"56","author":"Huang","year":"2017","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090910084182500_cit38","doi-asserted-by":"publisher","first-page":"13266","DOI":"10.1002\/anie.201807144","article-title":"Silver-Promoted Oxidative Benzylic C\u2013H Trifluoromethoxylation","volume":"57","author":"Yang","year":"2018","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026090910084182500_cit39","doi-asserted-by":"publisher","first-page":"1314","DOI":"10.1021\/ja00892a021","article-title":"The Effect\nof Fluorine Substitution on the Electronic Properties of Alkoxy, Alkylthio\nand Alkylsulfonyl Groups","volume":"85","author":"Sheppard","year":"1963","journal-title":"J. Am. Chem. Soc."},{"key":"2026090910084182500_cit40","doi-asserted-by":"publisher","first-page":"4993","DOI":"10.1002\/anie.201001704","article-title":"Straightforward\nSynthesis of Ethers: Metal-Free Reductive Coupling of Tosylhydrazones\nwith Alcohols or Phenols","volume":"49","author":"Barluenga","year":"2010","journal-title":"Angew. Chem., Int.\nEd."},{"key":"2026090910084182500_cit41","doi-asserted-by":"publisher","first-page":"7712","DOI":"10.1002\/anie.201601356","article-title":"Alkali Metal Carbenoids: A Case of Higher Stability\nof the Heavier Congeners","volume":"55","author":"Molitor","year":"2016","journal-title":"Angew. Chem., Int.\nEd."},{"key":"2026090910084182500_cit42","doi-asserted-by":"publisher","first-page":"13312","DOI":"10.1021\/acscatal.1c03949","article-title":"Modular Enantioselective\nSynthesis of cis-Cyclopropanes through Self-Sensitized\nStereoselective Photodecarboxylation\nwith Benzothiazolines","volume":"11","author":"Costantini","year":"2021","journal-title":"ACS Catal."},{"key":"2026090910084182500_cit43","doi-asserted-by":"publisher","first-page":"183","DOI":"10.1126\/science.adw4177","article-title":"Harnessing Carbene\nPolarity: Unified Catalytic Access to Donor, Neutral, and Acceptor\nCarbenes","volume":"389","author":"Nguyen","year":"2025","journal-title":"Science"},{"key":"2026090910084182500_cit44a","doi-asserted-by":"publisher","first-page":"288","DOI":"10.1021\/ar50140a004","article-title":"III The 1,2 Hydrogen\nShift: A Common\nVehicle for the Disappearance of Evanescent Molecular Species","volume":"12","author":"Schaefer","year":"1979","journal-title":"Acc. Chem. Res."},{"key":"2026090910084182500_cit44b","doi-asserted-by":"publisher","first-page":"8613","DOI":"10.1021\/ja00072a014","article-title":"1,2-Hydrogen Migration and Alkene Formation in the\nPhotoexcited States of Alkylphenyldiazomethanes","volume":"115","author":"Celebi","year":"1993","journal-title":"J. Am. Chem. Soc."},{"issue":"146","key":"2026090910084182500_cit44c","doi-asserted-by":"publisher","first-page":"23221","DOI":"10.1021\/jacs.4c05452","article-title":"Elusive Arylalkylcarbenes in Solution and in Crystals:\nFacile 1,2-R (R = H, Ph) Migrations of 1,2,2-Triphenylethylidene","volume":"146","author":"Fajardo","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"2026090910084182500_cit45","doi-asserted-by":"publisher","first-page":"25916","DOI":"10.1021\/jacs.6c04295","article-title":"Enantioselective\nB\u2013H Insertion of Branched \u03b1-Alkyl Carbenes","volume":"148","author":"Zhang","year":"2026","journal-title":"J. Am. Chem. Soc."},{"key":"2026090910084182500_cit46","doi-asserted-by":"publisher","first-page":"9921","DOI":"10.1039\/D4CS01269K","article-title":"The Influence of C\u2013F\u00b7\u00b7\u00b7H\u2013X Hydrogen-Bonding\nInteractions on the Reactivity and Selectivity of Organic Reactions","volume":"54","author":"Xu","year":"2025","journal-title":"Chem. Soc. Rev."},{"key":"2026090910084182500_cit47","doi-asserted-by":"publisher","first-page":"1312","DOI":"10.31635\/ccschem.023.202303282","article-title":"Radical\nArbuzov Reaction","volume":"6","author":"Chai","year":"2024","journal-title":"CCS Chem."}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c10096","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/35\/38080\/66628914\/jacs.6c10096.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/35\/38080\/66628914\/jacs.6c10096.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,9]],"date-time":"2026-09-09T15:27:50Z","timestamp":1788967670000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/35\/38080\/5260869\/Unlocking-Free-Trifluoromethoxy-Carbene-Reactivity"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,17]]},"references-count":78,"journal-issue":{"issue":"35","published-online":{"date-parts":[[2026,8,17]]},"published-print":{"date-parts":[[2026,9,9]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c10096","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,17]]}}}