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 -