Exploring the Activation Modes of a Rotaxane-Based Switchable Organocatalyst

被引：93

作者：

Blanco, Victor ^{[1
]}

Leigh, David A. ^{[1
]}

Lewandowska, Urszula ^{[1
]}

Lewandowsld, Bartosz ^{[1
]}

Marcos, Vanesa ^{[1
]}

机构：

[1] Univ Manchester, Sch Chem, Manchester M13 9PL, Lancs, England

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 44期

基金：

英国工程与自然科学研究理事会;

关键词：

DIELS-ALDER REACTIONS; ORGANO-SOMO CATALYSIS; ASYMMETRIC TRIENAMINE CATALYSIS; MOLECULAR MACHINE; ALPHA; BETA-UNSATURATED ALDEHYDES; ENANTIOSELECTIVE ORGANOCATALYSIS; TRIAZOLIUM STATION; MICHAEL ADDITION; DOMINO REACTIONS; VINYL SULFONES;

D O I：

10.1021/ja509236u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactivity of a rotaxane that acts as an aminocatalyst for the functionalization of carbonyl compounds through HOMO and LUMO activation pathways has been studied. Its catalytic activity is explored for C-C and C-S bond forming reactions through iminium catalysis, in nucleophilic substitutions and additions through enamine intermediates, in Diels-Alder reactions via trienamine catalysis, and in a tandem iminium-ion/enamine reaction. The catalyst can be switched "on" or "off", effectively controlling the rate of all of these chemical transformations, by the in situ change of the position of the macrocycle between two different binding sites on the rotaxane thread.

引用

页码：15775 / 15780

页数：6

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