The α-effect in cyclic secondary amines: new scaffolds for iminium ion accelerated transformations

被引：26

作者：

Brazier, John B. ^{[1
]}

Cavill, Julie L. ^{[1
]}

Elliott, Richard L. ^{[2
]}

Evans, Gareth ^{[1
]}

Gibbs, Timothy J. K. ^{[1
]}

Jones, Ian L. ^{[1
]}

Platts, James A. ^{[1
]}

Tomkinson, Nicholas C. O. ^{[1
]}

机构：

[1] Cardiff Univ, Sch Chem, Cardiff CF10 3AT, S Glam, Wales

[2] GlaxoSmithKline, Med Chem, Harlow CM19 5AW, Essex, England

来源：

TETRAHEDRON | 2009年 / 65卷 / 48期

基金：

英国工程与自然科学研究理事会;

关键词：

X-RAY; ALDER; ORGANOCATALYSIS; CATALYSIS; DESIGN; PHASE;

D O I：

10.1016/j.tet.2009.10.009

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Five-membered secondary amine heterocycles containing all alpha-heteroatom were prepared and shown to be ineffective as catalysts for the iminium ion catalysed Diels-Alder reaction between cinnamaldehyde and cyclopentadiene. Their six-membered counterparts proved to be highly active catalysts. In stark contrast, the catalytic activity observed when comparing the non alpha-heteroatom cyclic amines proline methyl ester and methyl pipecolinate showed the five-membered ring amine was significantly more active. Concurrent density functional theoretical calculations suggest a rationale for the observed trends in reactivity, highlighting that LUMO activation through all iminium ion intermediate plays a key role ill catalytic activity. (C) 2009 Elsevier Ltd. All rights reserved.

引用

页码：9961 / 9966

页数：6

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