Reaction of carboxylic acids with isocyanides: A mechanistic DFT study

被引：11

作者：

Marcelli, Tommaso ^{[1
]}

Himo, Fahmi ^{[1
]}

机构：

[1] Royal Inst Technol, Dept Theoret Chem, Sch Biotechnol, S-10691 Stockholm, Sweden

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2008年 / 2008卷 / 28期

基金：

瑞典研究理事会;

关键词：

density functional calculations; isocyanides; reaction mechanisms; E/Z isomerism; glycosylation;

D O I：

10.1002/ejoc.200800710

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

We present a computational investigation of the reaction between isocyanides and carboxylic acids. Our results indicate that this reaction begins with a stereoselective concerted alpha-addition of the acid to the isocyanide, leading exclusively to a Z-acyl imidate. Isomerization to the E isomer and successive rate-limiting 1,3 O -> N acyl migration yields an N-formyl imide. The calculated barriers are in good agreement with the experimental reaction conditions. Our results might provide an explanation for the peculiar reactivity observed when this reaction is carried out in a self-assembled capsule. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

引用

页码：4751 / 4754

页数：4

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