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.
Предметные области OECD FOS+WOS
- 1.05 НАУКИ О ЗЕМЛЕ И СМЕЖНЫЕ ЭКОЛОГИЧЕСКИЕ НАУКИ
- 1.06 БИОЛОГИЧЕСКИЕ НАУКИ
- 1.04 ХИМИЧЕСКИЕ НАУКИ