Chemodivergent aminocarbonylation enabled by oxygen vacancy-engineered Pd-doped In<sub>2</sub>O<sub>3</sub> nanocatalysts.
basic_science · Level V
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- Record sourced from PubMed, PMID 42361164.
- Also identified by DOI 10.1126/sciadv.aef9067.
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Abstract
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 α-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)-doped indium(III) oxide nanocatalysts by introducing oxygen vacancies (O<sub>v</sub>) to modulate the second-beyond coordination spheres (SBCSs) of Pd, and catalysts show excellent activity, selectivity, and reusability for synthesizing diverse amides and α-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.