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Chemodivergent aminocarbonylation enabled by oxygen vacancy-engineered Pd-doped In2O3 nanocatalysts
Shujuan Liu1, Teng Li1, Kang Zhao1
1State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, No. 18, Tianshui Middle Road, Lanzhou 730000, China.
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 (Ov) 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.
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