Nature of Electrogenerated Intermediates in Nitro-Substituted Nor-beta-lapachones: The Structure of Radical Species during Successive Electron Transfer in Multiredox Centers

作者：Armendariz Vidales Georgina; Hernandez Munoz Lindsay S; Gonzalez Felipe J; de Souza Antonio A; de Abreu Fabiane C; Jardim Guilherme A M; da Silva Eufranio N Jr; Goulart Marilia O F^*; Frontana Carlos

来源：Journal of Organic Chemistry, 2014, 79(11): 5201-5208.

DOI：10.1021/jo500787q

Electrochemical, spectroelectrochemical, and theoretical studies of the reduction reactions in nor-beta-lapachone derivatives including a nitro redox center showed that reduction of the compounds involves the formation of several radical intermediates, including a biradical dianion resultant from the separate reduction of the quinone and nitro groups in the molecules. Theoretical descriptions of the corresponding Fukui functions f(alpha alpha)(+) and f(beta beta)(+) and LUMO densities considering finite differences and frozen core approximations for describing the changes in electron and spin densities of the system allowed us to confirm these results. A description of the potential relationship with the obtained results and biological activity selectivity indexes suggests that both the formation of stable biradical dianion species and the stability of the serniquinone intermediates during further reduction are determining factors in the description of their biological activity.

• 出版日期2014-6-6