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Modulation of Prins Cyclization by Vibrational Strong Coupling.

Abstract

Light-molecule strong coupling has emerged within the last decade as an entirely new method to control chemical reactions. A few years ago it was discovered that the chemical reactivity could be altered by vibrational strong coupling (VSC). While the potential of VSC in organic chemistry appears enormous, only a limited number of reactions have been investigated under VSC to date, including solvolysis and deprotection reactions. Here we investigate the effect of VSC on a series of aldehydes and ketones undergoing Prins cyclization, an important synthetic step in pharmaceutical chemistry. We observe a decrease of the second-order rate constant with VSC of the reactant carbonyl stretching groups. We measure an increased activation energy due to VSC, but proportional changes in activation enthalpy and entropy suggest 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.

Authors+Show Affiliations

Hokkaido University, Research Institute for Electronic Science, North 20 West 10, Kita-ku, 001-0020, Sapporo, Hokkaido, JAPAN.Hokkaido University, Research Institute for Electronic Science, JAPAN.University of Melbourne, School of Chemistry, AUSTRALIA.Katholieke Universiteit Leuven, Department of Chemistry, BELGIUM.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31970847

Citation

Hirai, Kenji, et al. "Modulation of Prins Cyclization By Vibrational Strong Coupling." Angewandte Chemie (International Ed. in English), 2020.
Hirai K, Takeda R, Hutchison JA, et al. Modulation of Prins Cyclization by Vibrational Strong Coupling. Angew Chem Int Ed Engl. 2020.
Hirai, K., Takeda, R., Hutchison, J. A., & Uji-I, H. (2020). Modulation of Prins Cyclization by Vibrational Strong Coupling. Angewandte Chemie (International Ed. in English), doi:10.1002/anie.201915632.
Hirai K, et al. Modulation of Prins Cyclization By Vibrational Strong Coupling. Angew Chem Int Ed Engl. 2020 Jan 22; PubMed PMID: 31970847.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Modulation of Prins Cyclization by Vibrational Strong Coupling. AU - Hirai,Kenji, AU - Takeda,Rie, AU - Hutchison,James A, AU - Uji-I,Hiroshi, Y1 - 2020/01/22/ PY - 2019/12/07/received PY - 2020/01/15/accepted PY - 2020/01/15/revised PY - 2020/1/24/entrez KW - Prins cyclization KW - Rabi splitting KW - infrared spectroscopy KW - microcavity KW - vibrational strong coupling JF - Angewandte Chemie (International ed. in English) JO - Angew. Chem. Int. Ed. Engl. N2 - Light-molecule strong coupling has emerged within the last decade as an entirely new method to control chemical reactions. A few years ago it was discovered that the chemical reactivity could be altered by vibrational strong coupling (VSC). While the potential of VSC in organic chemistry appears enormous, only a limited number of reactions have been investigated under VSC to date, including solvolysis and deprotection reactions. Here we investigate the effect of VSC on a series of aldehydes and ketones undergoing Prins cyclization, an important synthetic step in pharmaceutical chemistry. We observe a decrease of the second-order rate constant with VSC of the reactant carbonyl stretching groups. We measure an increased activation energy due to VSC, but proportional changes in activation enthalpy and entropy suggest 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. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/31970847/Modulation_of_Prins_Cyclization_by_Vibrational_Strong_Coupling L2 - https://doi.org/10.1002/anie.201915632 DB - PRIME DP - Unbound Medicine ER -