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