Computational study on the catalytic control of endo/exo Diels-Alder reactions by cavity quantum vacuum fluctuations

Achieving control over chemical reaction's rate and stereoselectivity realizes one of the Holy Grails in chemistry that can revolutionize chemical and pharmaceutical industries. Strong light-matter interaction in optical or nanoplasmonic cavities might provide the knob to reach such control. In this work, we demonstrate the catalytic and selectivity control of an optical cavity for two selected Diels-Alder cycloaddition reactions using the quantum electrodynamics coupled cluster (QED-CC) method. Herein, we find that by changing the molecular orientation with respect to the polarization of the cavity mode the reactions can be significantly inhibited or selectively enhanced to produce major endo or exo products on demand. This work highlights the potential of utilizing quantum vacuum fluctuations of an optical cavity to modulate the rate of Diels-Alder cycloaddition reactions and to achieve stereoselectivity in a practical and non-intrusive way. We expect that the present findings will be applicable to a larger set of relevant reactions, including the click chemical reactions. Strong light-matter interactions are a pathway to chemical control at the molecular level. Here, authors theoretically show that an optical cavity allows to control catalysis, inhibition, and endo/exo stereoselectivity in Diels-Alder reactions.

Automated summary

This study demonstrates the catalytic and selectivity control of an optical cavity for Diels-Alder cycloaddition reactions using the QED-CC method. By changing the molecular orientation with respect to the cavity mode polarization, the reactions can be inhibited or selectively enhanced to produce specific endo/exo products. This work highlights the potential of utilizing quantum vacuum fluctuations of an optical cavity to modulate reaction rates and achieve stereoselectivity.