Articles producció científica> Química Física i Inorgànica

Remote 1,4-Carbon-to-Carbon Boryl Migration: From a Mechanistic Challenge to a Valuable Synthetic Application of Bicycles

  • Identification data

    Identifier: imarina:9363661
  • Authors:

    Dominguez-Molano P
    Solé-Daura A
    Carbó JJ
    Fernández E
    Advanced Science
    10.1002/advs.202309779
    Advanced Science. 11 (16):
  • Others:

    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: 2024-07-20
    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: http://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
  • Keywords:

    Biochemistry, Genetics and Molecular Biology (Miscellaneous),Chemical Engineering (Miscellaneous),Chemistry, Multidisciplinary,Engineering (Miscellaneous),Materials Science (Miscellaneous),Materials Science, Multidisciplinary,Medicine (Miscellaneous),Nanoscience & Nanotechnology,Physics and Astronomy (Miscellaneous)
    Simmons-smith
    Molecular calculations
    Mechanism
    Hydroxyboronate esters
    Effective core potentials
    Copper
    Boryl migration
    Bicycles
    Basis-sets
    Atoms
    Aryl
    Alkenes
    Aldehydes
    1,4-migration
    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)
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