Radical substitution with azide:: TMSN3-PhI(OAc)2 as a substitute of IN3

被引：77

作者：

Pedersen, CM ^{[1
]}

Marinescu, LG ^{[1
]}

Bols, M ^{[1
]}

机构：

[1] Aarhus Univ, Dept Chem, DK-8000 Aarhus, Denmark

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2005年 / 3卷 / 05期

关键词：

D O I：

10.1039/b500037h

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

TMSN3 and PhI(OAc)(2) were found to promote high-yield azide substitution of ethers, aldehydes and benzal acetals. The reaction is fast and occurs at zero to ambient temperature in acetonitrile. However, it is essential for the reaction that TMSN3 is added subsequent to the mixture of PhI(OAc)(2) and the substrate. A primary deuterium kinetic isotope effect was found for the azidonation of benzyl ethers both with TMSN3-PhI(OAc)(2) and with IN3. Also a Hammett free energy relationship study of this reaction showed good correlation with sigma(+) constants giving with p-values of -0.47 for TMSN3-PhI(OAc)(2) and 0.39 for IN3. On this basis a radical mechanism of the reaction was proposed.

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页码：816 / 822

页数：7

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