Pyridine Catalysis of Anhydride Hydrolysis within Carbodiimide‐Driven Reaction Networks

Baral, Renuka; Gunn, Jackson V.; Hartley, C. Scott

doi:10.1002/syst.202500042

Pyridine Catalysis of Anhydride Hydrolysis within Carbodiimide‐Driven Reaction Networks

Journal Article · Thu Sep 11 04:00:00 EDT 2025 · ChemSystemsChem

DOI:https://doi.org/10.1002/syst.202500042· OSTI ID:3000941

^[1]; Gunn, Jackson V. ^[1]; ^[1]

Miami University, Oxford, OH (United States)

Carbodiimide-fueled reaction networks offer a versatile platform for nonequilibrium chemical systems. Typically, the carbodiimide converts a carboxylic acid to its anhydride, called “activation,” which subsequently undergoes hydrolysis, called “deactivation.” Here, we investigate pyridines with variable nucleophilicity as catalysts to control deactivation (pyridine, 4-methylpyridine, 4-methoxypyridine, and 4-dimethylaminopyridine). Reactions have been monitored by NMR spectroscopy. Although this reaction network is simple, determination of well-defined rate constants from kinetic modeling is challenging because of correlation between the parameters. This issue can be addressed by analyzing the anhydride hydrolysis independently. The rate of attack of the pyridines on the anhydride follows expected nucleophilicity trends, although this is offset by increased protonation of more-nucleophilic pyridines at typical pH's. The optimized parameters can be used to model the full carbodiimide-driven process, although the presence of the common carbodiimide EDC has unanticipated effects on the anhydride hydrolysis rate. The results offer context for controlling carbodiimide-fueled reaction networks through the choice of suitable catalysts and pH.

View Accepted Manuscript (DOE)

Research Organization:: Miami University, Oxford, OH (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0018645

OSTI ID:: 3000941

Journal Information:: ChemSystemsChem, Journal Name: ChemSystemsChem; ISSN 2570-4206

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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