Toward Understanding CB[7]-Based Supramolecular Diels-Alder Catalysis

Dénes Berta; István Szabó; Oren A Scherman; Edina Rosta

doi:10.3389/fchem.2020.587084

Toward Understanding CB[7]-Based Supramolecular Diels-Alder Catalysis

Front Chem. 2020 Nov 6:8:587084. doi: 10.3389/fchem.2020.587084. eCollection 2020.

Authors

Dénes Berta^{1

2}, István Szabó², Oren A Scherman³, Edina Rosta^{1

2}

Affiliations

¹ Department of Physics and Astronomy, University College London, London, United Kingdom.
² Department of Chemistry, King's College London, London, United Kingdom.
³ Melville Laboratory for Polymer Synthesis, Department of Chemistry, University of Cambridge, Cambridge, United Kingdom.

Abstract

Cucurbiturils (CBs) are robust and versatile macrocyclic compounds, often used as molecular hosts in complex supramolecular systems. In previous work, remarkable catalytic activity has been observed for asymmetric cycloadditions under very mild conditions. Herein, we investigate the nature of supramolecular catalysis using DFT calculations and QM/MM techniques. We discuss induced conformational changes, electrostatic shielding effects from the highly polar aqueous environment and cooperativity in hydrogen bonding of the substrates in explicit water using QM/MM simulation techniques. Our results show little specificity for the chosen molecules, suggesting an excellent opportunity to expand the scope for catalytic use of these supramolecular macrocyclic containers.

Keywords: Diels-Alder (DA) chemistry; QM/MM; catalysis; confinement & solvent effect; quantum chemistry ab initio.