%0 Journal Article %A Lantaño, Beatriz %A Aguirre, José M. %A Drago, Eleonora V. %A Bollini, Mariela %A de la Faba, Diego J. %A Mufato, Jorge D. %D 2017 %T Synthesis of benzylidenecycloalkan-1-ones and 1,5-diketones under Claisen–Schmidt reaction: Influence of the temperature and electronic nature of arylaldehydes %U https://tandf.figshare.com/articles/journal_contribution/Synthesis_of_benzylidenecycloalkan-1-ones_and_1_5-diketones_under_Claisen-Schmidt_reaction_influence_of_the_temperature_and_electronic_nature_of_arylaldehydes/5393320 %R 10.6084/m9.figshare.5393320 %2 https://ndownloader.figshare.com/files/9282427 %K Aldolic condensation %K benzocycloalkan-1-ones %K bis-indane-1,5-diketones %K Michael addition %K spiropolycyclic-1,5-diketones %X

Herein, we present the results of the influence of reaction temperature and the electronic nature of arylaldehydes in the reactions of benzocycloalkan-1-ones and arylaldehydes under classical Claisen–Schmidt condensation conditions. The products obtained, 2-arylidene derivatives of benzocycloalkan-1-ones and/or spiropolycyclic-1,5-diketones through multicomponent reactions, depended on the electronic nature of arylaldehyde and the reaction temperature. Besides, under identical conditions, 2-arylideneindan-1-ones afforded bis-indane-1,5-diketones through a process that involves Michael addition reaction, which is also dependent on the temperature. Theoretical studies using density-functional theory allowed understanding the chemical reactivity and the site selectivity of α,β-enones used in this work through the calculation of global and local electrophilicity on C–β. Both the electrophilicity of C-β and the temperature led the course of reaction toward the formation of aldol condensation, aldol condensation/Michael addition, and aldol condensation/dimerization products. This work is the first to perform the structural and configurational assignments of bis-indane-1,5-diketones.

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