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Adv."],"published-print":{"date-parts":[[2026,6,26]]},"abstract":"<jats:p>\n                    The amide bond is a crucial structural motif in numerous bioactive natural products and pharmaceutical compounds. Mono- (MC) and double-aminocarbonylation (DC) are key methodologies for synthesizing aryl amides, including versatile \u03b1-ketoamides. However, selectively controlling MC and DC of aryl halides has been a long-standing challenge. Here, we report a previously unknown strategy to fully invert the selectivity from MC to DC in palladium (Pd)\u2013doped indium(III) oxide nanocatalysts by introducing oxygen vacancies (O\n                    <jats:sub>v<\/jats:sub>\n                    ) to modulate the second-beyond coordination spheres (SBCSs) of Pd, and catalysts show excellent activity, selectivity, and reusability for synthesizing diverse amides and \u03b1-ketoamides (130 examples). SBCS modulation drives long-range electron transfer to fine-tune electron localization, elongating Pd-O bonds, and weakening their strength to promote the second carbon monoxide adsorption and insertion for the DC pathway.\n                  <\/jats:p>","DOI":"10.1126\/sciadv.aef9067","type":"journal-article","created":{"date-parts":[[2026,6,26]],"date-time":"2026-06-26T17:59:33Z","timestamp":1782496773000},"update-policy":"https:\/\/doi.org\/10.34133\/aaas_crossmark","source":"Crossref","is-referenced-by-count":1,"title":["Chemodivergent aminocarbonylation enabled by oxygen vacancy\u2013engineered Pd-doped In\n                    <sub>2<\/sub>\n                    O\n                    <sub>3<\/sub>\n                    nanocatalysts"],"prefix":"10.1126","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0009-0000-7120-1166","authenticated-orcid":true,"given":"Shujuan","family":"Liu","sequence":"first","affiliation":[{"name":"State Key Laboratory of Low Carbon Catalysis and 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