Electrochemically site-selective alkoxylation of twisted 2-arylbenzoic acids via spirolactonization
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Título: | Electrochemically site-selective alkoxylation of twisted 2-arylbenzoic acids via spirolactonization |
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Autor/es: | Estruch Blasco, Manel | Bosque, Irene | Guijarro, David | Gonzalez-Gomez, Jose C. |
Grupo/s de investigación o GITE: | Nuevos Materiales y Catalizadores (MATCAT) |
Centro, Departamento o Servicio: | Universidad de Alicante. Departamento de Química Orgánica | Universidad de Alicante. Instituto Universitario de Síntesis Orgánica |
Palabras clave: | Electrochemical | Alkoxylation | 2-arylbenzoic acids | Spirolactonization |
Área/s de conocimiento: | Química Orgánica |
Fecha de publicación: | 20-jul-2021 |
Editor: | Royal Society of Chemistry |
Cita bibliográfica: | Organic Chemistry Frontiers. 2021, 8: 5130-5138. https://doi.org/10.1039/D1QO00834J |
Resumen: | The Electrochemical Cross-Dehydrogenative Coupling (ECDC) of twisted biphenyl-2-carboxylic acids with aliphatic alcohols provides 4′-alkoxyspirolactones which isomerize, under mild basic conditions, to give 4′-alkoxy-2-phenylbenzoic acids. This site-selective alkoxylation was readily adapted to 1 mmol scale and is environmentally friendly, as no terminal oxidants are needed and H2 is the only residue. The suitability of diphenic acid derivatives in this two-step protocol is noteworthy, especially for axially chiral substrates that can be functionalized with retention of the configuration and of the enantiomeric purity. We have proposed a plausible mechanism based on experimental pieces of evidence that support the single-electron oxidation of the carboxylate, formed by deprotonation of the biphenyl-2-carboxylic acids with 2,6-lutidine, and DFT calculations that suggest a very fast spirocyclization of the intermediate σ-aroyloxyl radical. Competing pathways to benzocoumarins were also examined by computational studies. |
Patrocinador/es: | This work was generously supported by the Spanish Ministerio de Ciencia, Innovación y Universidades (MICIU; grant no. CTQ2017-88171-P) and the University of Alicante (grant no. VIGROB-285/19). I. B. acknowledges the Spanish MICIU for a Juan de la Cierva-incorporación grant (no. IJCI-2017-33706). |
URI: | http://hdl.handle.net/10045/116823 |
ISSN: | 2052-4129 |
DOI: | 10.1039/D1QO00834J |
Idioma: | eng |
Tipo: | info:eu-repo/semantics/article |
Derechos: | © the Partner Organisations 2021 |
Revisión científica: | si |
Versión del editor: | https://doi.org/10.1039/D1QO00834J |
Aparece en las colecciones: | INV - MATCAT - Artículos de Revistas |
Archivos en este ítem:
Archivo | Descripción | Tamaño | Formato | |
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Estruch-Blasco_etal_2021_OrgChemFront_final.pdf | Versión final (acceso restringido) | 3,05 MB | Adobe PDF | Abrir Solicitar una copia |
Estruch-Blasco_etal_2021_OrgChemFront_preprint.pdf | Preprint (acceso abierto) | 862,04 kB | Adobe PDF | Abrir Vista previa |
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