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

被引：156

作者：

DiPoto, Maria C. ^{[1
]}

Hughes, Russell P. ^{[1
]}

Wu, Jimmy ^{[1
]}

机构：

[1] Dartmouth Coll, Dept Chem, Hanover, NH 03755 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2015年 / 137卷 / 47期

关键词：

CONCISE TOTAL-SYNTHESIS; ENANTIOSELECTIVE TOTAL-SYNTHESIS; CYCLOADDITION REACTIONS; EFFICIENT SYNTHESIS; CONSTRUCTION; CYCLIZATION; ALKALOIDS; CASCADE; DERIVATIVES; ALKYLATION;

D O I：

10.1021/jacs.5b10221

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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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页码：14861 / 14864

页数：4

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