Journal of Organic Chemistry, volume 87, issue 21, pages 13980-13989
Activation of O-Electrophiles via Structural and Solvent Effects: SN2@O Reaction of Cyclic Diacyl Peroxides with Enol Acetates
Vil’ Vera A.
1
,
Gorlov Evgenii S
1
,
Shuingalieva Diana V
1, 2
,
Kunitsyn Artem Yu
1
,
Krivoshchapov Nikolai V
1
,
Alabugin Igor V.
3
,
Publication type: Journal Article
Publication date: 2022-10-12
Journal:
Journal of Organic Chemistry
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 3.6
ISSN: 00223263, 15206904
Organic Chemistry
Abstract
The reactions of O-electrophiles, such as organic peroxides, with carbon nucleophiles are an umpolung alternative to the common approaches to C–O bond formation. Nucleophilic substitution at the oxygen atom of cyclic diacyl peroxides by enol acetates with the following deacylation leads to α-acyloxyketones with an appended carboxylic acid in 28–87% yields. The effect of fluorinated alcohols on the oxidative functionalization of enol acetates by cyclic diacyl peroxides was studied experimentally and computationally. Computational analysis reveals that the key step proceeds as a direct substitution nucleophilic bimolecular (SN2) reaction at oxygen (SN2@O). CF3CH2OH has a dual role in assisting in both steps of the reaction cascade: it lowers the energy of the SN2@O activation step by hydrogen bonding to a remote carbonyl and promotes the deacylation of the cationic intermediate.
Citations by journals
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2
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MolBank
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MolBank
2 publications, 66.67%
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Organometallics
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Organometallics
1 publication, 33.33%
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Citations by publishers
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Multidisciplinary Digital Publishing Institute (MDPI)
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Multidisciplinary Digital Publishing Institute (MDPI)
2 publications, 66.67%
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American Chemical Society (ACS)
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American Chemical Society (ACS)
1 publication, 33.33%
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1
2
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Vil’ V. A. et al. Activation of O-Electrophiles via Structural and Solvent Effects: SN2@O Reaction of Cyclic Diacyl Peroxides with Enol Acetates // Journal of Organic Chemistry. 2022. Vol. 87. No. 21. pp. 13980-13989.
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Vil’ V. A., Gorlov E. S., Shuingalieva D. V., Kunitsyn A. Yu., Krivoshchapov N. V., Medvedev M. G., Alabugin I. V., Terent'ev A. O. Activation of O-Electrophiles via Structural and Solvent Effects: SN2@O Reaction of Cyclic Diacyl Peroxides with Enol Acetates // Journal of Organic Chemistry. 2022. Vol. 87. No. 21. pp. 13980-13989.
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TY - JOUR
DO - 10.1021/acs.joc.2c01634
UR - https://doi.org/10.1021%2Facs.joc.2c01634
TI - Activation of O-Electrophiles via Structural and Solvent Effects: SN2@O Reaction of Cyclic Diacyl Peroxides with Enol Acetates
T2 - Journal of Organic Chemistry
AU - Vil’, Vera A.
AU - Gorlov, Evgenii S
AU - Shuingalieva, Diana V
AU - Kunitsyn, Artem Yu
AU - Krivoshchapov, Nikolai V
AU - Medvedev, Michael G.
AU - Alabugin, Igor V.
AU - Terent'ev, Alexander O.
PY - 2022
DA - 2022/10/12 00:00:00
PB - American Chemical Society (ACS)
SP - 13980-13989
IS - 21
VL - 87
SN - 0022-3263
SN - 1520-6904
ER -
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@article{2022_Vil’,
author = {Vera A. Vil’ and Evgenii S Gorlov and Diana V Shuingalieva and Artem Yu Kunitsyn and Nikolai V Krivoshchapov and Michael G. Medvedev and Igor V. Alabugin and Alexander O. Terent'ev},
title = {Activation of O-Electrophiles via Structural and Solvent Effects: SN2@O Reaction of Cyclic Diacyl Peroxides with Enol Acetates},
journal = {Journal of Organic Chemistry},
year = {2022},
volume = {87},
publisher = {American Chemical Society (ACS)},
month = {oct},
url = {https://doi.org/10.1021%2Facs.joc.2c01634},
number = {21},
pages = {13980--13989},
doi = {10.1021/acs.joc.2c01634}
}
Cite this
MLA
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Vil’, Vera A., et al. “Activation of O-Electrophiles via Structural and Solvent Effects: SN2@O Reaction of Cyclic Diacyl Peroxides with Enol Acetates.” Journal of Organic Chemistry, vol. 87, no. 21, Oct. 2022, pp. 13980-13989. https://doi.org/10.1021%2Facs.joc.2c01634.