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However, its further development has remained limited owing to stepwise radical and carbocationic pathways that induce side reactions and result in the loss of stereochemical information at the \u03b1-carbon. Here we demonstrate that this transformation can instead be realized through a concerted mechanism under Pd(II)\/Pd(IV) catalysis. The reaction proceeds through the formation of a six-membered Pd(IV) chelate, which undergoes fragmentation accompanied by \u03b2-to-\u03b1 carbon migration and carbon dioxide extrusion, with Pd(IV) serving as the redox centre. This closed-shell pathway enables precise stereochemical control: the migrating carbon retains its absolute configuration, whereas the \u03b1-stereocentre undergoes inversion. For unsymmetrical ketones, the reaction exhibits markedly higher migrating-group selectivity than the classical Tiffeneau\u2013Demjanov\n                    <jats:sup>2<\/jats:sup>\n                    and B\u00fcchner\u2013Curtius\u2013Schlotterbeck reactions\n                    <jats:sup>3<\/jats:sup>\n                    . Broadly applicable to cyclic and acyclic ketones and aldehydes, this method avoids hazardous diazo reagents. Its utility is illustrated by a concise total synthesis of (+)-rupestine D, in which the rearrangement serves as a key carbon-skeleton-editing step.\n                  <\/jats:p>","DOI":"10.1038\/s41586-026-11091-5","type":"journal-article","created":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T15:47:56Z","timestamp":1788450476000},"page":"666-672","update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Ketone homologation via palladium-catalysed decarboxylative rearrangement"],"prefix":"10.1038","volume":"658","author":[{"given":"Jing","family":"Gong","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qian","family":"Wang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8390-6689","authenticated-orcid":false,"given":"Jieping","family":"Zhu","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2026,9,3]]},"reference":[{"key":"11091_CR1","doi-asserted-by":"publisher","first-page":"2645","DOI":"10.1021\/ja01495a066","volume":"82","author":"EJ Corey","year":"1960","unstructured":"Corey, E. 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