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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Bibliographic Details
Published in:Angewandte Chemie International Edition 2021-03, Vol.60 (11), p.5712-5717
Main Authors: Sau, Abhijit, Nagarajan, Kalaivanan, Patrahau, Bianca, Lethuillier‐Karl, Lucas, Vergauwe, Robrecht M. A., Thomas, Anoop, Moran, Joseph, Genet, Cyriaque, Ebbesen, Thomas W.
Format: Article
Language:English
Subjects:
Charge transfer
Chemical reactions
Chemical Sciences
Communication
Communications
Coupled modes
Coupling
electrocyclic ring opening
or physical chemistry
orbital symmetry
pericyclic reactions
Ring opening
Selectivity
Stereoselectivity
strong coupling
Symmetry
Theoretical and
Woodward–Hoffmann rules
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Summary: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. Vacuum‐field strong coupling with molecular vibrations imposes symmetry constraints which alter the Woodward–Hoffmann selectivity of cyclobutene ring opening under thermal conditions.
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202013465