Dearomative Indole (3 + 2) Reactions with Azaoxyallyl Cations -- New Method for the Synthesis of Pyrroloindolines.

Herein, we report the first examples of the synthesis of pyrroloindolines by means of (3 + 2) dearomative annulation reactions between 3-substituted indoles and highly reactive azaoxyallyl cations. Computational studies using density functional theory (DFT) (B3LYP-D3/6-311G**++) support a stepwise r...

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Publicado en:Journal of the American Chemical Society Vol. 137; no. 47; pp. 14861 - 14865
Autores principales: DiPoto, Maria C., Hughes, Russell P., Wu, Jimmy
Formato: Artículo
Publicado: American Chemical Society 12/2/2015
Materias:
Acceso en línea:Ver este registro en EBSCOhost
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        atl: Dearomative Indole (3 + 2) Reactions with Azaoxyallyl Cations -- New Method for the Synthesis of Pyrroloindolines.
      aug:
        au:
          DiPoto, Maria C.
          Hughes, Russell P.
          Wu, Jimmy
        affil: Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, United States
      su:
        Indoline
        Cations
        Annulation
        Density functional theory
        Carbon-carbon bonds
      sug:
        subj:
          Indoline
          Cations
          Annulation
          Density functional theory
          Carbon-carbon bonds
      ab: Herein, we report the first examples of the synthesis of pyrroloindolines by means of (3 + 2) dearomative annulation reactions between 3-substituted indoles and highly reactive azaoxyallyl cations. Computational studies using density functional theory (DFT) (B3LYP-D3/6-311G**++) support a stepwise reaction pathway in which initial C-C bond formation takes place at C3 of indole, followed by ring closure to give the observed products. Insights gleaned from these calculations indicate that the solvent, either TFE or HFIP, can stabilize the transition state through H-bonding interactions with oxygen of the azaoxyallyl cation and other relevant intermediates, thereby increasing the rates of these reactions.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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          year: 2015
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