Electrogeneration of O-centered Radicals from N-alkoxyphthalimides and their use in δ-C-H functionalization. Comparison with the Photocatalytic Redox reaction
DOI:
https://doi.org/10.29356/jmcs.v70i1.2527Keywords:
Alkoxyl radicals, Organic electrosynthesis, N-alkoxyphthalimides (NAPIs), C-H allylation, δ-functionalizationAbstract
Abstract. The alkoxyl radicals have been proved to be useful synthetic intermediates in the δ-functionalization of C-H bonds, and their generation has progressed from the traditional harsh and toxic environments to benign reaction conditions provided by photoredox catalysis (PRC) and organic electrosynthesis (OES). This work describes the findings related to the reductive electrogeneration of oxygen-centered radicals from N-alkoxyphthalimides (NAPIs) and their use in remote C-H allylation. In this approach, the use of pulsed alternating polarity electrolysis, Hantzsch ester in the presence of δ-terpinene as a proton donor and hydrogen donor, respectively, in combination of an allyl sulfone led us to achieve the consecutive cathodic reduction, N-O cleavage, 1,5-hydrogen atom transfer, and radical allylation. Finally, the synthesized NAPIs were subjected to standard photocatalytic redox conditions, yielding comparable results.
Resumen. Los radicales alcoxilo han demostrado ser intermediarios sintéticos útiles en la funcionalización δ de enlaces C–H, y su generación ha evolucionado desde ambientes tradicionales severos y tóxicos hacia condiciones de reacción benignas proporcionadas por la catálisis fotoredox y la electroquímica orgánica. Este trabajo describe los hallazgos relacionados con la electrogeneración reductiva de radicales centrados en oxígeno a partir de N-alcoxiftalimidas y su uso en la alilación remota de enlaces C–H. En este estudio, el uso de electrólisis con polaridad alternante pulsada, éster de Hantzsch en presencia de γ-terpineno como donadores de protón e hidrógeno, respectivamente, en combinación con una alilsulfona, nos permitió lograr la reducción catódica, ruptura del enlace N–O, transferencia de átomo de hidrógeno 1,5 y alilación radicalaria. Finalmente, las N-alcoxiftalimidas sintetizadas se hicieron reaccionar en condiciones estándar de catálisis foto-redox, obteniéndose resultados comparables.
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Copyright (c) 2026 Edgar A. Colindres-Diaz, Diego Francisco Chicas-Baños, Julio Romero-Ibañez, Bernardo Antonio Frontana-Uribe
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