Articles producció científica> Química Física i Inorgànica

Mapping the Electronic Structure and the Reactivity Trends for Stabilized alpha-Boryl Carbanions

  • Datos identificativos

    Identificador: imarina:9225155
    Autores:
    Maza, Ricardo J.Fernandez, ElenaCarbo, Jorge J.
    Resumen:
    The chemistry of stabilized alpha-boryl carbanions shows remarkable diversity, and can enable many different synthetic routes towards efficient C-C bond formation. The electron-deficient, trivalent boron center stabilizes the carbanion facilitating its generation and tuning its reactivity. Here, the electronic structure and the reactivity trends of a large dataset of alpha-boryl carbanions are described. DFT-derived parameters were used to capture their electronic and steric properties, computational reactivity towards model substrates, and crystallographic analysis within the Cambridge Structural Dataset. This study maps the reactivity space by systematically varying the nature of the boryl moiety, the substituents of the carbanionic center, the number of alpha-boryl motifs, and the metal counterion. In general, the free carbanionic intermediates are described as borata-alkene species with C-B pi interactions polarized towards the carbon. Furthermore, it was possible to classify the alpha-boryl alkylidene metal precursors into three classes directly related to their reactivity: 1) nucleophilic borata-alkene salts with alkali and alkaline earth metals, 2) nucleophilic eta(2)-(C-B) borata-alkene complexes with early transition metals, Cu and Ag, and 3) alpha-boryl alkyl complexes with late transition metals. This trend map aids selection of the appropriate reactive synthon depending on the reactivity sought.
  • Otros:

    Autor según el artículo: Maza, Ricardo J.; Fernandez, Elena; Carbo, Jorge J.;
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: Carbó Martin, Jorge Juan / Fernández Gutiérrez, Maria Elena / Maza Quiroga, Ricardo José
    Palabras clave: Transition metals Transition metal compounds Substrates Steric properties Reactivity trends Ray crystal-structure Polarization functions Organic-synthesis Olefins Molecular calculations Main-group elements Late transition metals Large dataset Ions Hindered organoboron groups Electronic structure Electron-deficient Effective core potentials Early transition metals Dimesitylboron group Diastereoselective synthesis Descriptors Derived parameters Density functional calculations Crystallographic analysis Chemical bonds Carbanionic centers Borata Basis-sets Alpha-borylcarbanion Alkalinity
    Resumen: The chemistry of stabilized alpha-boryl carbanions shows remarkable diversity, and can enable many different synthetic routes towards efficient C-C bond formation. The electron-deficient, trivalent boron center stabilizes the carbanion facilitating its generation and tuning its reactivity. Here, the electronic structure and the reactivity trends of a large dataset of alpha-boryl carbanions are described. DFT-derived parameters were used to capture their electronic and steric properties, computational reactivity towards model substrates, and crystallographic analysis within the Cambridge Structural Dataset. This study maps the reactivity space by systematically varying the nature of the boryl moiety, the substituents of the carbanionic center, the number of alpha-boryl motifs, and the metal counterion. In general, the free carbanionic intermediates are described as borata-alkene species with C-B pi interactions polarized towards the carbon. Furthermore, it was possible to classify the alpha-boryl alkylidene metal precursors into three classes directly related to their reactivity: 1) nucleophilic borata-alkene salts with alkali and alkaline earth metals, 2) nucleophilic eta(2)-(C-B) borata-alkene complexes with early transition metals, Cu and Ag, and 3) alpha-boryl alkyl complexes with late transition metals. This trend map aids selection of the appropriate reactive synthon depending on the reactivity sought.
    Áreas temáticas: Química Organic chemistry Medicina i Materiais Interdisciplinar General medicine General chemistry Farmacia Engenharias iii Engenharias ii Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Biotecnología Biodiversidade Astronomia / física
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    Direcció de correo del autor: ricardojose.maza@estudiants.urv.cat ricardojose.maza@estudiants.urv.cat j.carbo@urv.cat mariaelena.fernandez@urv.cat
    Identificador del autor: 0000-0002-3945-6721 0000-0001-9025-1791
    Fecha de alta del registro: 2024-07-27
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    Enlace a la fuente original: https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.202101464
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Chemistry-A European Journal. 27 (48): 12352-12361
    Referencia de l'ítem segons les normes APA: Maza, Ricardo J.; Fernandez, Elena; Carbo, Jorge J.; (2021). Mapping the Electronic Structure and the Reactivity Trends for Stabilized alpha-Boryl Carbanions. Chemistry-A European Journal, 27(48), 12352-12361. DOI: 10.1002/chem.202101464
    DOI del artículo: 10.1002/chem.202101464
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2021
    Tipo de publicación: Journal Publications
  • Palabras clave:

    Catalysis,Chemistry,Chemistry (Miscellaneous),Chemistry, Multidisciplinary,Organic Chemistry
    Transition metals
    Transition metal compounds
    Substrates
    Steric properties
    Reactivity trends
    Ray crystal-structure
    Polarization functions
    Organic-synthesis
    Olefins
    Molecular calculations
    Main-group elements
    Late transition metals
    Large dataset
    Ions
    Hindered organoboron groups
    Electronic structure
    Electron-deficient
    Effective core potentials
    Early transition metals
    Dimesitylboron group
    Diastereoselective synthesis
    Descriptors
    Derived parameters
    Density functional calculations
    Crystallographic analysis
    Chemical bonds
    Carbanionic centers
    Borata
    Basis-sets
    Alpha-borylcarbanion
    Alkalinity
    Química
    Organic chemistry
    Medicina i
    Materiais
    Interdisciplinar
    General medicine
    General chemistry
    Farmacia
    Engenharias iii
    Engenharias ii
    Ciências biológicas iii
    Ciências biológicas ii
    Ciências biológicas i
    Ciências agrárias i
    Chemistry, multidisciplinary
    Chemistry (miscellaneous)
    Chemistry (all)
    Chemistry
    Catalysis
    Biotecnología
    Biodiversidade
    Astronomia / física
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