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Herein, we present the copper-catalyzed atom transfer radical addition (ATRA) of alkyl halides to alkenylphosphonates for the synthesis of \u03b1-halophosphonates enabled by 1,1\u2032-azobis(cyclohexanecarbonitrile) (ACHN). Mechanistic investigations support that the diazo compound serves as an in situ reducing agent regenerating [Cu(I)] throughout the reaction and enabling high turnover numbers. Under the optimized conditions, a broad scope of radical precursors, including primary, secondary, and tertiary haloalkanes add to substituted vinylphosphonates in good to excellent yields. Product derivatization demonstrates the synthetic utility of the reaction.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c03586","type":"journal-article","created":{"date-parts":[[2026,9,22]],"date-time":"2026-09-22T11:03:31Z","timestamp":1790075011000},"page":"12407-12412","source":"Crossref","is-referenced-by-count":0,"title":["Synthesis of\n\u03b1-Halophosphonates via Copper-Catalyzed\nAtom Transfer Radical Addition"],"prefix":"10.1021","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0009-0008-7815-9157","authenticated-orcid":true,"given":"Jacob A.","family":"Utley","sequence":"first","affiliation":[{"name":"The University of Texas at Austin , , 105 East 24th Street , , ,","place":["Austin, Texas, United States, 78712"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tam D.","family":"Ho","sequence":"additional","affiliation":[{"name":"The University of Texas at Austin , , 105 East 24th Street , , ,","place":["Austin, Texas, United States, 78712"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0078-7865","authenticated-orcid":true,"given":"Byung Joo","family":"Lee","sequence":"additional","affiliation":[{"name":"The University of Texas at Austin , , 105 East 24th Street , , ,","place":["Austin, Texas, United States, 78712"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jake R.","family":"Elliott","sequence":"additional","affiliation":[{"name":"The University of Texas at Austin , , 105 East 24th Street , , ,","place":["Austin, Texas, United States, 78712"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Saurabh S.","family":"Satpute","sequence":"additional","affiliation":[{"name":"The University of Texas at Austin , , 105 East 24th Street , , ,","place":["Austin, Texas, United States, 78712"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3102-2686","authenticated-orcid":true,"given":"Kami L.","family":"Hull","sequence":"additional","affiliation":[{"name":"The University of Texas at Austin , , 105 East 24th Street , , ,","place":["Austin, Texas, United States, 78712"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,22]]},"reference":[{"issue":"4793","key":"2026100208364199000_cit1","doi-asserted-by":"publisher","first-page":"1173","DOI":"10.1126\/science.2434996","article-title":"Why Nature\nChose Phosphates","volume":"235","author":"Westheimer","year":"1987","journal-title":"Science"},{"issue":"1","key":"2026100208364199000_cit2","doi-asserted-by":"publisher","first-page":"71","DOI":"10.1016\/S0021-9258(18)72218-7","article-title":"The Equilibria\nof Isomerase and Aldolase, and the Problem\nof the Phosphorylation of Glyceraldehyde Phosphate","volume":"149","author":"Meyerhof","year":"1943","journal-title":"J. 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