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Substituents effects in the Diels-Alder reaction of 1,1-difluoronaphthalen-2(1H)-ones with cyclopentadiene. / Dyan, Ok Ton; Andreev, Rodion V.; Zaikin, Pavel A.
в: Journal of Fluorine Chemistry, Том 250, 109859, 10.2021.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Substituents effects in the Diels-Alder reaction of 1,1-difluoronaphthalen-2(1H)-ones with cyclopentadiene
AU - Dyan, Ok Ton
AU - Andreev, Rodion V.
AU - Zaikin, Pavel A.
N1 - Funding Information: This research was supported by the Russian Foundation for Basic Research, Project 19-33-60101. Authors thank the Multi-Access Chemical Research Centre SB RAS at N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS for spectral analysis and Novosibirsk State University Supercomputer center (NUSC) for computational resources. Funding Information: This research was supported by the Russian Foundation for Basic Research , Project 19-33-60101 . Authors thank the Multi-Access Chemical Research Centre SB RAS at N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS for spectral analysis and Novosibirsk State University Supercomputer center (NUSC) for computational resources. Publisher Copyright: © 2021
PY - 2021/10
Y1 - 2021/10
N2 - 1,1-difluoronaphthalen-2(1H)-ones are promising fluorine-containing building blocks due to the possibility of multiple-site functionalization. The Diels-Alder reaction is one of the powerful approaches to construction of complex saturated rigid three-dimensional structures or polyaromatic compounds. Being readily available through the electrophilic fluorodearomatization of substituted naphthalene-2-ols, the naphthalenones are good models to elucidate the structural effects on the rate and selectivity of the Diels-Alder reaction. Moderate reactivity and high diastereoselectivity of cycloaddition reaction of 1,1-difluoronaphthalen-2(1H)-ones allow careful investigation of the substituent effects. In this paper we determined the rate constants for the cycloaddition reaction to compare the reactivity of the dienophiles under study. We experimentally explored the substituents effects on the rate and the selectivity of [4+2]-cycloaddition. A quantum chemical approach was used to rationalize the results obtained and predict the substituents effect on the reactivity of dienophiles. Performed correlation analysis demonstrated a relation between the substituent's constants and the reactivity of corresponding dienophiles in the reaction with cyclopentadiene.
AB - 1,1-difluoronaphthalen-2(1H)-ones are promising fluorine-containing building blocks due to the possibility of multiple-site functionalization. The Diels-Alder reaction is one of the powerful approaches to construction of complex saturated rigid three-dimensional structures or polyaromatic compounds. Being readily available through the electrophilic fluorodearomatization of substituted naphthalene-2-ols, the naphthalenones are good models to elucidate the structural effects on the rate and selectivity of the Diels-Alder reaction. Moderate reactivity and high diastereoselectivity of cycloaddition reaction of 1,1-difluoronaphthalen-2(1H)-ones allow careful investigation of the substituent effects. In this paper we determined the rate constants for the cycloaddition reaction to compare the reactivity of the dienophiles under study. We experimentally explored the substituents effects on the rate and the selectivity of [4+2]-cycloaddition. A quantum chemical approach was used to rationalize the results obtained and predict the substituents effect on the reactivity of dienophiles. Performed correlation analysis demonstrated a relation between the substituent's constants and the reactivity of corresponding dienophiles in the reaction with cyclopentadiene.
KW - Activation strain model
KW - Diastereoselectivity
KW - Diels-Alder cycloaddition
KW - Organofluorine compounds
KW - Substituents effects
UR - http://www.scopus.com/inward/record.url?scp=85112777391&partnerID=8YFLogxK
U2 - 10.1016/j.jfluchem.2021.109859
DO - 10.1016/j.jfluchem.2021.109859
M3 - Article
AN - SCOPUS:85112777391
VL - 250
JO - Journal of Fluorine Chemistry
JF - Journal of Fluorine Chemistry
SN - 0022-1139
M1 - 109859
ER -
ID: 33979691