Cavity Catalysis of an Enantioselective Reaction under Vibrational Strong Coupling

Abstract

AbstractStrong light‐matter interaction is emerging as an exciting tool for controlling chemical reactions. Here, we demonstrate an L‐proline‐catalyzed direct asymmetric Aldol reaction under vibrational strong coupling. Both the reactants (4‐nitrobenzaldehyde and acetone) carbonyl bands are coupled to an infrared photon and react in the presence of L‐proline. The reaction mixture is eluted from the cavity, and the conversion yields and enantiomeric excess are quantified using NMR and chiral HPLC. The conversion yields increase by up to 90 % in ON‐resonance conditions. Interestingly, a large increase in the conversion yield does not affect the enantiomeric excess. Further control experiments were carried out by varying the temperature, and we propose that the rate‐limiting step may not be the deciding factor in enantioselectivity. Whereas the formation of the enamine intermediate is modified by cavity coupling experiments. For this class of enantioselective reactions, strong coupling does not change the enantiomeric excess, possibly due to the large energy difference in chiral transition states. Strong coupling can boost the formation of enamine intermediate, thereby favouring the product yield. This gives more hope to test polaritonic chemistry based on enantioselective reactions in which the branching ratios can be controlled.