Substituents effects in the Diels-Alder reaction of 1,1-difluoronaphthalen-2(1H)-ones with cyclopentadiene

Ok Ton Dyan, Rodion V. Andreev, Pavel A. Zaikin

Research output: Contribution to journalArticlepeer-review

Abstract

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.

Original languageEnglish
Article number109859
JournalJournal of Fluorine Chemistry
Volume250
DOIs
Publication statusPublished - Oct 2021

Keywords

  • Activation strain model
  • Diastereoselectivity
  • Diels-Alder cycloaddition
  • Organofluorine compounds
  • Substituents effects

OECD FOS+WOS

  • 1.05 EARTH AND RELATED ENVIRONMENTAL SCIENCES
  • 1.06 BIOLOGICAL SCIENCES
  • 1.04 CHEMICAL SCIENCES

Fingerprint

Dive into the research topics of 'Substituents effects in the Diels-Alder reaction of 1,1-difluoronaphthalen-2(1H)-ones with cyclopentadiene'. Together they form a unique fingerprint.

Cite this