Molecular cages are sought after as receptors and catalysts. However, typical dynamic covalent chemistry approaches restrict the shape-persistence, solubility and stability of self-assembled organic cages. As a result, organic cages occupy a narrow chemical and functional space, and solution-phase applications and studies remain rare. We report an in situ trapping protocol, using Pinnick oxidation conditions, to convert soluble metastable imine assemblies to robust amide cages, and exemplify the method to access previously inaccessible organic cages. The new cages are internally functionalised with two constrained and diametrically opposed carboxylic acid groups that can distinguish between functionalised piperazines in THF. We anticipate our approach will broaden access to robust, soluble, self-assembled organic cages of an unsymmetrical or semi-flexible nature, which in turn will drive advances in solution-phase applications of molecular cages.
Keywords: Pinnick oxidation; cage crystal structure; host-guest chemistry; molecular recognition; organic cages.
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.