Author, as appears in the article.: Maza, Ricardo J.; Fernandez, Elena; Carbo, Jorge J.;

Department: Química Física i Inorgànica

URV's Author/s: Carbó Martin, Jorge Juan / Fernández Gutiérrez, Maria Elena / Maza Quiroga, Ricardo José

Keywords: 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

Abstract: 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.

Thematic Areas: 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

licence for use: https://creativecommons.org/licenses/by/3.0/es/

Author's mail: mariaelena.fernandez@urv.cat j.carbo@urv.cat ricardojose.maza@estudiants.urv.cat

Author identifier: 0000-0001-9025-1791 0000-0002-3945-6721

Record's date: 2023-09-02

Papper version: info:eu-repo/semantics/publishedVersion

Link to the original source: https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.202101464

Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/

Papper original source: Chemistry-A European Journal. 27 (48): 12352-12361

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

Article's DOI: 10.1002/chem.202101464

Entity: Universitat Rovira i Virgili

Journal publication year: 2021

Publication Type: Journal Publications