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Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity

  • Dades identificatives

    Identificador: imarina:9389633
    Autors:
    Dorel, RuthEchavarren, Antonio M
    Resum:
    Gold(I) complexes are the most effective catalysts for the electrophilic activation of alkynes under homogeneous conditions, and a broad range of versatile synthetic tools have been developed for the construction of carbon-carbon or carbon-heteroatom bonds. The properties of gold (I) complexes can be easily tuned sterically or electronically depending on the ligand, consequently modulating their reactivity in the activation of alkynes, alkenes, and allenes. Reactions catalyzed by gold (I) are similar to those catalyzed by other electrophilic metal complexes or even BrOønsted acids and resemble carbocation-mediated processes. However, gold (I) provides unique control on complex transformations by very selectively activating alkynes and by stabilizing the key carbocationic intermediates by weak, but still significant, metal to carbene πback-donation. Additionally, the structural characteristics of linear two-coordinated gold (I) complexes, in which the ligand is very distant from the nucleophilic addition site to the πbound substrate, explains the slow development of general enantioselective transformations of alkynes.
  • Altres:

    Autor segons l'article: Dorel, Ruth; Echavarren, Antonio M
    Departament: Química Analítica i Química Orgànica
    Autor/s de la URV: ECHAVARREN PABLOS, ANTONIO
    Paraules clau: Ugi intramolecular hydroarylation Silyl enol ethers One-pot synthesis N-heterocyclic carbene Migration/intramolecular 3+2 cycloaddition Highly diastereoselective formation Gold-catalyzed cycloisomerization Enantioselective total-synthesis Dynamic solution behavio Abnormal nhc-gold(i) complexes
    Resum: Gold(I) complexes are the most effective catalysts for the electrophilic activation of alkynes under homogeneous conditions, and a broad range of versatile synthetic tools have been developed for the construction of carbon-carbon or carbon-heteroatom bonds. The properties of gold (I) complexes can be easily tuned sterically or electronically depending on the ligand, consequently modulating their reactivity in the activation of alkynes, alkenes, and allenes. Reactions catalyzed by gold (I) are similar to those catalyzed by other electrophilic metal complexes or even BrOønsted acids and resemble carbocation-mediated processes. However, gold (I) provides unique control on complex transformations by very selectively activating alkynes and by stabilizing the key carbocationic intermediates by weak, but still significant, metal to carbene πback-donation. Additionally, the structural characteristics of linear two-coordinated gold (I) complexes, in which the ligand is very distant from the nucleophilic addition site to the πbound substrate, explains the slow development of general enantioselective transformations of alkynes.
    Àrees temàtiques: Química Materiais General medicine General chemistry Farmacia Engenharias iii Engenharias ii Ciências biológicas ii Ciências biológicas i Ciência de alimentos Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Biotecnología
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    Adreça de correu electrònic de l'autor: antoniomaria.echavarren@urv.cat
    Identificador de l'autor: 0000-0002-6418-7930
    Data d'alta del registre: 2024-11-09
    Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
    Referència a l'article segons font original: Chemical Reviews. 115 (17): 9028-9072
    Referència de l'ítem segons les normes APA: Dorel, Ruth; Echavarren, Antonio M (2015). Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity. Chemical Reviews, 115(17), 9028-9072. DOI: 10.1021/cr500691k
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2015
    Tipus de publicació: Journal Publications
  • Paraules clau:

    Chemistry,Chemistry (Miscellaneous),Chemistry, Multidisciplinary
    Ugi intramolecular hydroarylation
    Silyl enol ethers
    One-pot synthesis
    N-heterocyclic carbene
    Migration/intramolecular 3+2 cycloaddition
    Highly diastereoselective formation
    Gold-catalyzed cycloisomerization
    Enantioselective total-synthesis
    Dynamic solution behavio
    Abnormal nhc-gold(i) complexes
    Química
    Materiais
    General medicine
    General chemistry
    Farmacia
    Engenharias iii
    Engenharias ii
    Ciências biológicas ii
    Ciências biológicas i
    Ciência de alimentos
    Chemistry, multidisciplinary
    Chemistry (miscellaneous)
    Chemistry (all)
    Chemistry
    Biotecnología
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