Dearomative Indole (3 + 2) Reactions with Azaoxyallyl Cations--New Method for the Synthesis of Pyrroloindolines.
J Am Chem Soc
; 137(47): 14861-4, 2015 Dec 02.
Article
en En
| MEDLINE
| ID: mdl-26562355
ABSTRACT
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.
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1
Bases de datos:
MEDLINE
Asunto principal:
Pirroles
/
Reacción de Cicloadición
/
Indoles
Idioma:
En
Revista:
J Am Chem Soc
Año:
2015
Tipo del documento:
Article
País de afiliación:
Estados Unidos