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In this study, we report a two-step carbonyl-to-sulfur (CO-to-S) atom swap approach, enabled by a rationally designed\n                    <jats:italic toggle=\"yes\">N<\/jats:italic>\n                    \u2032-alkyl-hydrazonamide (NAHA) reagent that promotes forming pre-aromatic intermediates twice sequentially by different mechanisms, thereby achieving homolytic cleavage of both \u03b1-C\u2212C bonds of the ketone substrates. A Ts\u2212S\u2212Ts (Ts,\n                    <jats:italic toggle=\"yes\">p<\/jats:italic>\n                    -toluenesulfonyl) reagent mediates this process through successive intermolecular and intramolecular alkyl radical trapping by the central sulfur. This method shows a broad substrate scope and excellent chemoselectivity, providing a streamlined route to sulfur-containing scaffolds from readily available ketones.\n                  <\/jats:p>","DOI":"10.1126\/science.adx2723","type":"journal-article","created":{"date-parts":[[2025,6,12]],"date-time":"2025-06-12T14:00:16Z","timestamp":1749736816000},"page":"1436-1440","update-policy":"https:\/\/doi.org\/10.34133\/aaas_crossmark","source":"Crossref","is-referenced-by-count":41,"title":["Carbonyl-to-sulfur swap enabled by sequential double carbon-carbon bond activation"],"prefix":"10.1126","volume":"388","author":[{"ORCID":"https:\/\/orcid.org\/0009-0001-4954-6771","authenticated-orcid":true,"given":"Zining","family":"Zhang","sequence":"first","affiliation":[{"name":"Department of Chemistry, University of Chicago, Chicago, IL, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1331-6015","authenticated-orcid":true,"given":"Guangbin","family":"Dong","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Chicago, Chicago, IL, USA."}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"221","reference":[{"key":"e_1_3_2_2_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-018-0021-z"},{"key":"e_1_3_2_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.3c00219"},{"key":"e_1_3_2_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.2c00797"},{"key":"e_1_3_2_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.7b02088"},{"key":"e_1_3_2_6_2","doi-asserted-by":"publisher","DOI":"10.1038\/s44160-022-00052-1"},{"key":"e_1_3_2_7_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.adj5331"},{"key":"e_1_3_2_8_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.adq6245"},{"key":"e_1_3_2_9_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41586-023-06613-4"},{"key":"e_1_3_2_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1SC06968C"},{"key":"e_1_3_2_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c08464"},{"key":"e_1_3_2_12_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-023-01428-2"},{"key":"e_1_3_2_13_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-023-40979-3"},{"key":"e_1_3_2_14_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.abg5526"},{"key":"e_1_3_2_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm901241e"},{"key":"e_1_3_2_16_2","doi-asserted-by":"publisher","DOI":"10.1007\/s41061-018-0184-5"},{"key":"e_1_3_2_17_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature08356"},{"key":"e_1_3_2_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm400807n"},{"key":"e_1_3_2_19_2","unstructured":"H. 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