Synthesis of benzylidenecycloalkan-1-ones and 1,5-diketones under Claisen–Schmidt reaction: Influence of the temperature and electronic nature of arylaldehydes

Autor: Eleonora V. Drago, Jorge D. Mufato, Diego J. de la Faba, Mariela Bollini, B. Lantano, J. M. Aguirre
Rok vydání: 2017
Předmět:
Zdroj: Synthetic Communications. 47:2202-2214
ISSN: 1532-2432
0039-7911
DOI: 10.1080/00397911.2017.1367819
Popis: 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. Fil: Lantaño, Beatriz. Universidad Nacional de Luján; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina Fil: Aguirre, José M.. Universidad Nacional de Luján; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina Fil: Drago, Eleonora V.. Universidad Nacional de Luján; Argentina Fil: Bollini, Mariela. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; Argentina Fil: de la Faba, Diego J.. Universidad Nacional de Luján; Argentina Fil: Mufato, Jorge Domingo. Universidad Nacional de Luján; Argentina
Databáze: OpenAIRE
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