Diazo Esters as Dienophiles in Intramolecular (4 + 2) Cycloadditions: Computational Explorations of Mechanism.

The first experimental examples of Diels-Alder (DA) reactions of diazo compounds as heterodienophiles with dienes have been studied with density functional theory (DFT) using the M06-2X functional. For comparison, the reactivities of diazo esters as dienophiles or 1,3-dipoles with 1,3-dienes in inte...

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Publicado en:Journal of the American Chemical Society Vol. 139; no. 7; pp. 2766 - 2771
Autores principales: Abing Duan, Peiyuan Yu, Fang Liu, Huang Qiu, Feng Long Gu, Doyle, Michael P., Houk, K. N.
Formato: Artículo
Publicado: American Chemical Society 2/22/2017
Materias:
Acceso en línea:Ver este registro en EBSCOhost
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        atl: Diazo Esters as Dienophiles in Intramolecular (4 + 2) Cycloadditions: Computational Explorations of Mechanism.
      aug:
        au:
          Abing Duan
          Peiyuan Yu
          Fang Liu
          Huang Qiu
          Feng Long Gu
          Doyle, Michael P.
          Houk, K. N.
        affil:
          Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education; School of Chemistry and Environment, South China Normal University, Guangzhou 510006, China
          Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, United States
          Department of Chemistry, The University of Texas at San Antonio, San Antonio, Texas 78249, United States
      su:
        Diazo compounds
        Ring formation (Chemistry)
        Diels-Alder reaction
        Dienophiles
        Density functional theory
      sug:
        subj:
          Diazo compounds
          Ring formation (Chemistry)
          Diels-Alder reaction
          Dienophiles
          Density functional theory
      ab: The first experimental examples of Diels-Alder (DA) reactions of diazo compounds as heterodienophiles with dienes have been studied with density functional theory (DFT) using the M06-2X functional. For comparison, the reactivities of diazo esters as dienophiles or 1,3-dipoles with 1,3-dienes in intermolecular model systems have been analyzed by the distortion/interaction model. The 1,3-dipolar cycloaddition is strongly favored for the intermolecular system. The intramolecular example is unique because the tether strongly favors the (4 + 2) cycloaddition.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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