Switching Pathways: Room-Temperature Neutral Solvolysis and Substitution of Amides

被引：106

作者：

Hutchby, Marc ^{[1
]}

Houlden, Chris E.

Haddow, Mairi F. ^{[1
]}

Tyler, Simon N. G. ^{[2
]}

Lloyd-Jones, Guy C. ^{[1
]}

Booker-Milburn, Kevin I. ^{[1
]}

机构：

[1] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England

[2] CatScI Ltd, AstraZeneca, Avlon Works, Cardiff CF3 2PX, S Glam, Wales

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2012年 / 51卷 / 02期

基金：

英国工程与自然科学研究理事会;

关键词：

amides; solvolysis; steric hindrance; substituent effects; substitution; ACYL TRANSFER-REACTIONS; N-ARYL-LACTAMS; TWISTED AMIDE; DISTORTED AMIDES; PEPTIDE-BOND; HYDROLYSIS; KINETICS; PURIFICATION; MECHANISM; RESONANCE;

D O I：

10.1002/anie.201107117

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Stick or twist: By introducing steric hindrance at the nitrogen atom, stable linear amides bearing an electron-withdrawing α-substituent (Z=Ar, PhSO2, P(O)(OR)2, CN, or CO2R) can be induced to undergo solvolysis and substitution reactions through an elimination-addition mechanism (see picture). Key to this process is a low barrier to rotation around the amide bond and the α-substituentZ. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：548 / 551

页数：4

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