Distortion/Interaction Analysis Reveals the Origins of Selectivities in Iridium-Catalyzed C-H Borylation of Substituted Arenes and 5-Membered Heterocycles.

The iridium-catalyzed borylation of mono- and disubstituted arenes and heteroarenes has been studied with density functional theory. The distortion/interaction model was employed to understand the origins of selectivities in these reactions. Computations revealed that the transition states for C-H o...

Descripción completa

Detalles Bibliográficos
Publicado en:Journal of the American Chemical Society Vol. 136; no. 12; pp. 4575 - 4584
Autores principales: Green, Aaron G., Peng Liu, Merlic, Craig A., Houk, K. N.
Formato: Artículo
Publicado: American Chemical Society 3/26/2014
Materias:
Acceso en línea:Ver este registro en EBSCOhost
fields @attributes:
  recordID: 1
pdfLink:
plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=95575368&site=ehost-live
header:
  @attributes:
    shortDbName: hlh
    uiTerm: 95575368
    longDbName: Humanities International Complete
    uiTag: AN
  controlInfo:
    bkinfo:
    jinfo:
      jid:
        00027863
        ACS
      jtl: Journal of the American Chemical Society
      issn: 00027863
      maglogo: N
    pubinfo:
      dt: 3/26/2014
      vid: 136
      iid: 12
      pid: 997
      pub: American Chemical Society
    artinfo:
      ui:
        95575368
        10.1021/ja411699u
      ppf: 4575
      ppct: 9
      formats:
      tig:
        atl: Distortion/Interaction Analysis Reveals the Origins of Selectivities in Iridium-Catalyzed C-H Borylation of Substituted Arenes and 5-Membered Heterocycles.
      aug:
        au:
          Green, Aaron G.
          Peng Liu
          Merlic, Craig A.
          Houk, K. N.
        affil: Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States
      su:
        Iridium catalysts
        Density functional theory
        Carbon-hydrogen bonds
        Heteroarenes
        Aromatic compounds
        Transition state theory (Chemistry)
        Oxidative addition
        Regioselectivity (Chemistry)
      sug:
        subj:
          Iridium catalysts
          Density functional theory
          Carbon-hydrogen bonds
          Heteroarenes
          Aromatic compounds
          Transition state theory (Chemistry)
          Oxidative addition
          Regioselectivity (Chemistry)
      ab: The iridium-catalyzed borylation of mono- and disubstituted arenes and heteroarenes has been studied with density functional theory. The distortion/interaction model was employed to understand the origins of selectivities in these reactions. Computations revealed that the transition states for C-H oxidative addition are very late, resembling the aryl iridium hydride intermediate with a fully formed Ir-C bond. Consequently, the regioselectivity is mainly controlled by differences in the interaction energies between the iridium catalyst and arene carbon.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
    refInfo:
    copyright:
      @attributes:
        flag: Y
      dt:
        @attributes:
          year: 2014
    holdings:
      @attributes:
        islocal: N