Autor según el artículo: Dominguez-Molano P; Solé-Daura A; Carbó JJ; Fernández E
Departamento: Química Física i Inorgànica
Autor/es de la URV: Carbó Martin, Jorge Juan / Fernández Gutiérrez, Maria Elena / Fernández López, Elena
Palabras clave: Simmons-smith Molecular calculations Mechanism Hydroxyboronate esters Effective core potentials Copper Boryl migration Bicycles Basis-sets Atoms Aryl Alkenes Aldehydes 1,4-migration
Resumen: The present paper reports a remote carbon-to-carbon boryl migration via an intramolecular 1,4-B/Cu shift, which establishes an in situ stereospecific electrophilic trap on the alkene moiety. The synthetic application is developed to prepare functionalized cyclopentenes by means of a palladium-catalyzed regioselective intramolecular coupling that completes a strategic cyclopropanation and generates valuable structural bicyclic systems. The mechanism is characterized by DFT (density functional theory) calculations which showed that the 1,4-migration proceeds through an intramolecular, nucleophilic attack of the copper-alkyl moiety on the boron atom bonded to the C(sp2), leading to a 5-membered boracycle structure. The computation of the 1,3- and 1,4-B/Cu shifts is also compared as is the impact of the endo- or exocyclic alkene on the reaction kinetics.The intramolecular 1,4-B/Cu shift justifies the observed remote carbon-to-carbon boryl migration, which makes stereoselective electrophilic trapping on the alkene moiety possible. Subsequent palladium-catalyzed regioselective intramolecular coupling enables functionalized cyclopentenes to be prepared that complete strategic cyclopropanation and deliver structurally valuable bicyclic systems. DFT mechanistic studies show that remote boryl migration occurs efficiently through 5-membered boracycle intermediates. image
Áreas temáticas: Physics and astronomy (miscellaneous) Physics and astronomy (all) Nanoscience & nanotechnology Medicine (miscellaneous) Materials science, multidisciplinary Materials science (miscellaneous) Materials science (all) General physics and astronomy General materials science General engineering General chemical engineering Engineering (miscellaneous) Engineering (all) Chemistry, multidisciplinary Chemical engineering (miscellaneous) Chemical engineering (all) Biochemistry, genetics and molecular biology (miscellaneous)
Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
Direcció de correo del autor: mariaelena.fernandez@urv.cat j.carbo@urv.cat
Identificador del autor: 0000-0001-9025-1791 0000-0002-3945-6721
Fecha de alta del registro: 2024-05-11
Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
Enlace a la fuente original: https://onlinelibrary.wiley.com/doi/full/10.1002/advs.202309779
URL Documento de licencia: http://repositori.urv.cat/ca/proteccio-de-dades/
Referencia al articulo segun fuente origial: Advanced Science. 11 (16):
Referencia de l'ítem segons les normes APA: Dominguez-Molano P; Solé-Daura A; Carbó JJ; Fernández E (2024). Remote 1,4-Carbon-to-Carbon Boryl Migration: From a Mechanistic Challenge to a Valuable Synthetic Application of Bicycles. Advanced Science, 11(16), -. DOI: 10.1002/advs.202309779
DOI del artículo: 10.1002/advs.202309779
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2024
Tipo de publicación: Journal Publications
Repositori URV