A Mild, Catalyst-free C—N Exchange Platform Based on Zwitterionic Quinone Transamination

Abstract

Reversible amine-aldehyde chemistry has enabled the synthesis of diverse Schiff-base materials, including cages, polymers, and covalent organic frameworks, but the hydrolytic lability of imine linkages motivates the search for alternative amine-based reversible reactions that generate more stable materials. Here, we report zwitterionic quinone transamination as a mild, catalyst-free C—N exchange platform based on p-quinoneimines. Time-resolved ¹H NMR spectroscopy shows clean sequential conversion of C3/C3-ZQ to the mixed C3/C4-ZQ product and then to C4/C4-ZQ, while kinetic analysis reveals the statistical behavior expected for a two-site substrate. Density functional theory (DFT) calculations support a stepwise nucleophilic addition-proton-transfer/reorganization-elimination pathway involving Meisenheimer-type intermediates. Beyond pairwise exchange, mixtures of primary amines generate multicomponent zwitterionic quinone libraries with near-statistical distributions under soluble conditions. Solvent-coupled phase behavior further biases product distributions and enables enrichment of less-soluble longer-chain zwitterionic quinones. The chemistry is also compatible with interfacial self-assembly, where amine input leads to preferential adsorption of one formed zwitterionic quinone at the TCB/HOPG interface. This work establishes quinoneimine transamination as a quantitatively tractable C—N exchange chemistry for constitutional reorganization and provides a foundation for developing zwitterionic polymers and covalent organic frameworks.

Keywords

Zwitterionic quinone / Transamination / Dynamic covalent chemistry

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