Preparation of iodonium ylides: probing the fluorination of 1,3-dicarbonyl compounds with a fluoroiodane

被引：39

作者：

Geary, Gemma C. ^{[1
]}

Hope, Eric G. ^{[1
]}

Singh, Kuldip ^{[1
]}

Stuart, Alison M. ^{[1
]}

机构：

[1] Univ Leicester, Dept Chem, Leicester LE1 7RH, Leics, England

来源：

RSC ADVANCES | 2015年 / 5卷 / 21期

关键词：

INTRAMOLECULAR AMINOFLUORINATION; CATALYZED FLUORINATION; HF; CRYSTAL;

D O I：

10.1039/c4ra15733h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The isolation of iodonium ylide 8, from the reaction of fluoroiodane 1 with ethyl 3-oxo-3phenylpropanoate 5 in the presence of potassium fluoride, provides strong evidence that 1,3-dicarbonyl compounds undergo an addition reaction with fluoroiodane 1 to form an iodonium intermediate which can be deprotonated to generate an iodonium ylide. In the presence of TREAT-HF, however, the iodonium intermediate reacts to form the 2-fluoro-1,3-dicarbonyl product and we propose that fluoroiodane 1 simulates electrophilic fluorination via an addition/substitution mechanism. Further evidence to support this mechanism was obtained by successfully reacting the isolated iodonium ylide 8 with TREAT-HF, hydrochloric acid, acetic acid and p-toluenesulfonic acid to form the 2-fluoro-, 2-chloro-, 2-acetyl-and 2-tosyl-1,3-ketoesters respectively.

引用

页码：16501 / 16506

页数：6

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