Issue 10, 2022

Zirconium oxo clusters as discrete molecular catalysts for the direct amide bond formation

Abstract

Zirconium compounds are prime catalysts in organic synthesis; however, their utility is often diminished by their moisture sensitivity. Here, we investigate zirconium oxo cluster (ZrOC) [Zr6(OH)4O4(OAcr)12]2 (OAcr = acrylate) (Zr12), as an air and moisture stable molecular catalyst for the atom economic formation of amide bonds directly from non-activated carboxylic acids and amines. The Zr12 is readily prepared in one step from commercially available zirconium salts and carboxylic acids, and unlike the majority of metal complexes developed so far, it catalyzes the intermolecular formation of various amides in high yields without requiring water scavenging, inert or anhydrous reactions conditions, or any additives. Detailed mechanistic evaluation through control and NMR experiments suggests that the Zr12 cluster, rather than a lower nuclearity species, is the catalytic active species involved in the reaction. Further, a comparison of Zr12 performance with previously reported ZrCl4 under the same conditions showcases several advantages of Zr12 over conventional catalysts, underlining the potential of ZrOC as a new class of practical, readily available, and stable catalysts.

Graphical abstract: Zirconium oxo clusters as discrete molecular catalysts for the direct amide bond formation

Supplementary files

Article information

Article type
Paper
Submitted
02 Mar 2022
Accepted
29 Mar 2022
First published
30 Mar 2022

Catal. Sci. Technol., 2022,12, 3190-3201

Zirconium oxo clusters as discrete molecular catalysts for the direct amide bond formation

Y. Zhang, F. de Azambuja and T. N. Parac-Vogt, Catal. Sci. Technol., 2022, 12, 3190 DOI: 10.1039/D2CY00421F

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