biostudies-literatureSau AEuropean Research CouncilAgence Nationale de la RechercheH2020 Marie Skłodowska-Curie Actions5712-5717https://www.ebi.ac.uk/biostudies/studies/S-EPMC7986062biostudies-literatureUnknown60(11)Vibrational strong coupling (VSC) has recently been shown to change the rate and chemoselectivity of ground-state chemical reactions via the formation of light-matter hybrid polaritonic states. However, the observation that vibrational-mode symmetry has a large influence on charge-transfer reactions under VSC suggests that symmetry considerations could be used to control other types of chemical selectivity through VSC. Here, we show that VSC influences the stereoselectivity of the thermal electrocyclic ring opening of a cyclobutene derivative, a reaction which follows the Woodward-Hoffmann rules. The direction of the change in stereoselectivity depends on the vibrational mode that is coupled, as do changes in rate and reaction thermodynamics. These results on pericyclic reactions confirm tAngewandte Chemie (International ed. in English)Modifying Woodward-Hoffmann Stereoselectivity Under Vibrational Strong Coupling.PMC7986062639170ANR-10-EQPX-52-01ANR-10-LABX- 0026 CSCANR-18-QUAN-0005-01792101788482Patrahau BEbbesen TWVergauwe RMAGenet CSau AThomas ALethuillier-Karl LNagarajan KMoran JfalseModifying Woodward-Hoffmann Stereoselectivity Under Vibrational Strong Coupling.Vibrational strong coupling (VSC) has recently been shown to change the rate and chemoselectivity of ground-state chemical reactions via the formation of light-matter hybrid polaritonic states. However, the observation that vibrational-mode symmetry has a large influence on charge-transfer reactions under VSC suggests that symmetry considerations could be used to control other types of chemical selectivity through VSC. Here, we show that VSC influences the stereoselectivity of the thermal electrocyclic ring opening of a cyclobutene derivative, a reaction which follows the Woodward-Hoffmann rules. The direction of the change in stereoselectivity depends on the vibrational mode that is coupled, as do changes in rate and reaction thermodynamics. These results on pericyclic reactions confirm t2021-01-01T00:00:00Z2021 Mar2025-04-04T20:35:24.901Z2025-04-04T20:35:24.901ZS-EPMC79860623330586410.1002/anie.202013465