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

Dénes Berta, István Szabó, Oren A. Scherman, Edina Rosta^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

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.

Original language	English
Article number	587084
Journal	Frontiers in Chemistry
Volume	8
DOIs	https://doi.org/10.3389/fchem.2020.587084
Publication status	Published - 6 Nov 2020

Keywords

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

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10.3389/fchem.2020.587084

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title = "Toward Understanding CB[7]-Based Supramolecular Diels-Alder Catalysis",

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.",

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T1 - Toward Understanding CB[7]-Based Supramolecular Diels-Alder Catalysis

AU - Berta, Dénes

AU - Szabó, István

AU - Scherman, Oren A.

AU - Rosta, Edina

PY - 2020/11/6

Y1 - 2020/11/6

N2 - 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.

AB - 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.

KW - catalysis

KW - confinement & solvent effect

KW - Diels-Alder (DA) chemistry

KW - QM/MM

KW - quantum chemistry ab initio

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DO - 10.3389/fchem.2020.587084

M3 - Article

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VL - 8

JO - Frontiers in Chemistry

JF - Frontiers in Chemistry

M1 - 587084

ER -

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

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Keywords

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