Premium
Modifying Woodward–Hoffmann Stereoselectivity Under Vibrational Strong Coupling
Author(s) -
Sau Abhijit,
Nagarajan Kalaivanan,
Patrahau Bianca,
LethuillierKarl Lucas,
Vergauwe Robrecht M. A.,
Thomas Anoop,
Moran Joseph,
Genet Cyriaque,
Ebbesen Thomas W.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202013465
Subject(s) - pericyclic reaction , stereoselectivity , chemistry , cyclobutene , molecular vibration , computational chemistry , chemical physics , photochemistry , ring (chemistry) , molecule , organic chemistry , catalysis
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.