title: A Computational Study of Structure and Reactivity of N-Substitued-4-Piperidones Curcumin Analogues and Their Radical Anions.
abstract: In this work, a computational study of a series ofN-substitued-4-piperidones curcumin analogues is presented. The molecular structure of the neutral molecules and their radical anions, as well as their reactivity, are investigated.N-substituents include methyl and benzyl groups, while substituents on the aromatic rings cover electron-donor and electron-acceptor groups. Substitutions at the nitrogen atom do not significantly affect the geometry and frontier molecular orbitals (FMO) energies of these molecules. On the other hand, substituents on the aromatic rings modify the distribution of FMO. In addition, they influence the capability of these molecules to attach an additional electron, which was studied through adiabatic (AEA) and vertical electron affinities (VEA), as well as vertical detachment energy (VDE). To study electrophilic properties of these structures, local reactivity indices, such as Fukui (f⁺) and Parr (P⁺) functions, were calculated, and show the influence of the aromatic rings substituents on the reactivity of α,β-unsaturated ketones towards nucleophilic attack. This study has potential implications for the design of curcumin analogues based on a 4-piperidone core with desired reactivity.
authors.affiliation: Programa Institucional de Fomento a la Investigación, Desarrollo e Innovación, Universidad Tecnológica Metropolitana, Ignacio Valdivieso 2409, Casilla 9845, Santiago 8940577, Chile. mmartinez@utem.cl.
authors.forename: Maximiliano
authors.initials: M
authors.lastname: Martínez-Cifuentes
authors.affiliation: Departamento de Química, Facultad de Ciencias, Universidad de Chile, Las Palmeras 3425, Casilla 653, Santiago 7800003, Chile. bweiss@uchile.cl.
authors.forename: Boris
authors.initials: B
authors.lastname: Weiss-López
authors.affiliation: Instituto de Química de Recursos Naturales, Universidad de Talca, Av. Lircay s/n, Casilla 747, Talca 3460000, Chile. raraya@utalca.cl.
authors.forename: Ramiro
authors.initials: R
authors.lastname: Araya-Maturana
mesh_terms: D000838:Anions / Q000737:chemistry; D002623:Chemistry Techniques, Analytical; D019295:Computational Biology; D003474:Curcumin / Q000031:analogs & derivatives* / Q000737:chemistry*; D004583:Electrons; D008958:Models, Molecular; D010881:Piperidones / Q000737:chemistry*
chemical_list: D000838:Anions; D010881:Piperidones; D003474:Curcumin
keywords: 4-piperidone; computational chemistry; curcumin; radical anion; reactivity indices