Author, as appears in the article.: Dominguez-Molano P; Solé-Daura A; Carbó JJ; Fernández E
Department: Química Física i Inorgànica
URV's Author/s: Carbó Martin, Jorge Juan / Fernández Gutiérrez, Maria Elena / Fernández López, Elena
Keywords: Simmons-smith Molecular calculations Mechanism Hydroxyboronate esters Effective core potentials Copper Boryl migration Bicycles Basis-sets Atoms Aryl Alkenes Aldehydes 1,4-migration
Abstract: 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
Thematic Areas: 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)
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: j.carbo@urv.cat mariaelena.fernandez@urv.cat
Author identifier: 0000-0002-3945-6721 0000-0001-9025-1791
Record's date: 2024-08-03
Papper version: info:eu-repo/semantics/publishedVersion
Link to the original source: https://onlinelibrary.wiley.com/doi/full/10.1002/advs.202309779
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Advanced Science. 11 (16):
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
Article's DOI: 10.1002/advs.202309779
Entity: Universitat Rovira i Virgili
Journal publication year: 2024
Publication Type: Journal Publications