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H-Bonded Counterion-Directed Catalysis: Enantioselective Gold(I)-Catalyzed Addition to 2-Alkynyl Enones as a Case Study

  • Identification data

    Identifier: imarina:9280122
    Authors:
    Marti, AlexMontesinos-Magraner, MarcEchavarren, Antonio M.Franchino, Allegra
    Abstract:
    H-bonded counterion-directed catalysis (HCDC) is a strategy wherein a chiral anion that is hydrogen-bonded to the achiral ligand of a metal complex is responsible for enantioinduction. In this article we present the application of H-bonded counterion-directed catalysis to the Au(I)-catalyzed enantioselective tandem cycloisomerization-addition reaction of 2-alkynyl enones. Following the addition of C-, N- or O-centered nucleophiles, bicyclic furans were obtained in moderate to excellent yield and enantioselectivity (28 examples, 59-96 % yield, 62 : 38 to 95 : 5 er). The optimal catalytic system, comprising a phosphinosquaramide Au(I) chloride complex and a BINOL-derived phosphoramidate Ag(I) salt, was selected in a combinatorial fashion from a larger library with the help of high-throughput screening. An enantioselectivity switch of ca. 120 Delta ee% was observed upon addition of the achiral Au(I) component to the Ag(I) salt.
  • Others:

    Author, as appears in the article.: Marti, Alex; Montesinos-Magraner, Marc; Echavarren, Antonio M.; Franchino, Allegra;
    Department: Química Analítica i Química Orgànica
    URV's Author/s: ECHAVARREN PABLOS, ANTONIO / Martí Zaragoza, Àlex / Montesinos Magraner, Marc
    Keywords: Ynenones Transfer hydrogenation Platinum Ligands Hydrogen bonding Highly substituted furans Gold complexes Gold Cycloisomerization Cycloaddition Cyclization Chiral counterion Chiral anions Asymmetric catalysis 2-(1-alkynyl)-2-alken-1-ones
    Abstract: H-bonded counterion-directed catalysis (HCDC) is a strategy wherein a chiral anion that is hydrogen-bonded to the achiral ligand of a metal complex is responsible for enantioinduction. In this article we present the application of H-bonded counterion-directed catalysis to the Au(I)-catalyzed enantioselective tandem cycloisomerization-addition reaction of 2-alkynyl enones. Following the addition of C-, N- or O-centered nucleophiles, bicyclic furans were obtained in moderate to excellent yield and enantioselectivity (28 examples, 59-96 % yield, 62 : 38 to 95 : 5 er). The optimal catalytic system, comprising a phosphinosquaramide Au(I) chloride complex and a BINOL-derived phosphoramidate Ag(I) salt, was selected in a combinatorial fashion from a larger library with the help of high-throughput screening. An enantioselectivity switch of ca. 120 Delta ee% was observed upon addition of the achiral Au(I) component to the Ag(I) salt.
    Thematic Areas: Química Physical and theoretical chemistry Organic chemistry Materiais Interdisciplinar Farmacia Engenharias ii Ciências biológicas iii Ciências biológicas ii Ciências agrárias i Ciência de alimentos Chemistry, organic Biotecnología Biodiversidade Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: antoniomaria.echavarren@urv.cat alex.marti@estudiants.urv.cat
    Author identifier: 0000-0002-6418-7930
    Record's date: 2024-09-07
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/ejoc.202200518
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: European Journal Of Organic Chemistry. 2022 (38):
    APA: Marti, Alex; Montesinos-Magraner, Marc; Echavarren, Antonio M.; Franchino, Allegra; (2022). H-Bonded Counterion-Directed Catalysis: Enantioselective Gold(I)-Catalyzed Addition to 2-Alkynyl Enones as a Case Study. European Journal Of Organic Chemistry, 2022(38), -. DOI: 10.1002/ejoc.202200518
    Article's DOI: 10.1002/ejoc.202200518
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2022
    Publication Type: Journal Publications
  • Keywords:

    Chemistry, Organic,Organic Chemistry,Physical and Theoretical Chemistry
    Ynenones
    Transfer hydrogenation
    Platinum
    Ligands
    Hydrogen bonding
    Highly substituted furans
    Gold complexes
    Gold
    Cycloisomerization
    Cycloaddition
    Cyclization
    Chiral counterion
    Chiral anions
    Asymmetric catalysis
    2-(1-alkynyl)-2-alken-1-ones
    Química
    Physical and theoretical chemistry
    Organic chemistry
    Materiais
    Interdisciplinar
    Farmacia
    Engenharias ii
    Ciências biológicas iii
    Ciências biológicas ii
    Ciências agrárias i
    Ciência de alimentos
    Chemistry, organic
    Biotecnología
    Biodiversidade
    Astronomia / física
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