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Modulation of Prins Cyclization by Vibrational Strong Coupling
Author(s) -
Hirai Kenji,
Takeda Rie,
Hutchison James A.,
Ujii Hiroshi
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201915632
Subject(s) - chemistry , cycloaddition , enthalpy , reactivity (psychology) , solvolysis , computational chemistry , molecule , chemical reaction , reaction rate constant , photochemistry , organic chemistry , thermodynamics , kinetics , catalysis , medicine , physics , alternative medicine , pathology , quantum mechanics , hydrolysis
Light‐molecule strong coupling has emerged within the last decade as a new method to control chemical reactions. A few years ago it was discovered that chemical reactivity could be altered by vibrational strong coupling (VSC). Only a limited number of reactions have been investigated under VSC to date, including solvolysis and deprotection reactions. Here the effect of VSC on a series of aldehydes and ketones undergoing Prins cyclization, an important synthetic step in pharmaceutical chemistry, is investigated. A decrease of the second‐order rate constant with VSC of the reactant carbonyl stretching groups is observed. We also observe an increased activation energy due to VSC, but proportional changes in activation enthalpy and entropy, suggesting no substantive change in reaction pathway. The addition of common cycloaddition reactions to the stable of VSC‐modified chemical reactions is another step towards establishing VSC as a genuine tool for synthetic chemistry.