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Achieving control over chemical reaction's rate and stereoselectivityrealizes one of the Holy Grails in chemistry that can revolutionize chemicaland pharmaceutical industries. Strong light-matter interaction in optical ornanoplasmonic cavities might provide the knob to reach such control. In thiswork, we demonstrate the catalytic and selectivity control of an optical cavityfor two selected Diels-Alder cycloaddition reactions using the quantumelectrodynamics coupled cluster (QED-CC) method. Herein, we find that bychanging the molecular orientation with respect to the polarization of thecavity mode the reactions can be significantly inhibited or selectivelyenhanced to produce major endo or exo products on demand. This work highlightsthe potential of utilizing quantum vacuum fluctuations of an optical cavity tomodulate the rate of Diels-Alder cycloaddition reactions and to achievestereoselectivity in a practical and non-intrusive way. We expect that thepresent findings will be applicable to a larger set of relevant click chemicalreactions under strong light-matter coupling conditions.

Catalysis in Click Chemistry Reactions Controlled by Cavity Quantum Vacuum Fluctuations: The Case of endo/exo Diels-Alder Reaction