CAGED

Despite the fact that over 85% of chemical production relies on catalysis, achieving high selectivity remains a significant challenge. Currently, enzymes are unrivaled in their ability to control regioselectivity and stereoselectivity, yet they suffer from high costs, low stability, and limited applicability to non-native substrates. On the other hand, traditional heterogeneous catalysts, such as zeolites, offer improved selectivity through pore fine-tuning but are often restricted by structural rigidity and diffusion limits for large molecules. To bridge this gap, supramolecular “caged catalysis” has emerged as a powerful strategy, using molecular capsules or surfactant aggregates to create a second solvation sphere. This confinement mimics enzymatic environments, allowing for precise substrate orientation and intermediate stabilization, though the field still seeks more flexible and structurally diverse systems.

The primary objective of the CAGED project is to develop a comprehensive approach to supramolecular catalysis by confining reagents and catalysts within specifically designed cage-forming systems. By integrating extra flexibility with structural precision, the project aims to empower both new and existing catalysts with enzyme-like substrate selectivity and regioselectivity.The strategy relies on three distinct self-organized systems: surfactant aggregates for low-cost compartmentalization in water, monolayer-protected gold nanoparticles for precise spatial control of functional groups, and resorcinarene-based self-assembled capsules to maximize non-covalent interactions. This modular nature ensures that complex catalytic environments can be produced through simple synthetic steps and easily tuned libraries.
To achieve these goals, the project will combine organometallic catalysts, such as Pd(II) complexes, and organic catalysts with the selected cage systems to facilitate successful molecular recognition and trapping.

This methodology will be rigorously tested across a broad range of relevant organic reactions, including allylic substitutions, cycloadditions, and Baeyer-Villiger oxidations. By creating an ideal nanoreactor where non-covalent interactions are amplified, CAGED seeks to ensure both the efficient conversion of substrates and the subsequent release of products. Ultimately, the project aims to demonstrate that high structural and functional complexity can be achieved through simple self-assembly procedures, providing a cost-effective alternative to traditional enzyme engineering.

Indane synthesis in resorcinarene capsules: The crucial role of the carbocation counter anion

This study elucidates the pivotal role of hexameric capsule C in the Brønsted acid-catalyzed dimerization of styrenes to indanes. The confined environment significantly influences the reaction outcomes and requires the co-encapsulation of acid counter-anions for the effective stabilization of carbocation intermediates. These results indicate the potential to optimize the catalytic activity of hexameric capsule C through careful selection of suitable carbocation counter-anions.

Chin. Chem. Lett. 2025, 112261