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Modifying 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...

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Detalles Bibliográficos
Autores principales: Sau, Abhijit, Nagarajan, Kalaivanan, Patrahau, Bianca, Lethuillier‐Karl, Lucas, Vergauwe, Robrecht M. A., Thomas, Anoop, Moran, Joseph, Genet, Cyriaque, Ebbesen, Thomas W.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7986062/
https://www.ncbi.nlm.nih.gov/pubmed/33305864
http://dx.doi.org/10.1002/anie.202013465
Descripción
Sumario: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 that symmetry plays a key role in chemistry under VSC.