Azodicarboxamides as Template Binding Motifs for the Building of Hydrogen-Bonded Molecular Shuttles

被引:94
作者
Berna, Jose [1 ]
Alajarin, Mateo [1 ]
Orenes, Raul-Angel [2 ]
机构
[1] Univ Murcia, Dept Quim Organ, Fac Quim, E-30100 Murcia, Spain
[2] Univ Murcia, SAI, E-30100 Murcia, Spain
关键词
MITSUNOBU REACTION; PHOSPHORIC-ACID; DRIVEN; ROTAXANES; CRYSTAL; MECHANISM; MACHINES; 1,1-AZOBISFORMAMIDE; PHOTOISOMERIZATION; DECOMPOSITION;
D O I
10.1021/ja101151t
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Azodicarboxamides (R2NCON=NCONR2) are shown to act as new templates for the assembly of unprecedented azo-functionalized hydrogen-bond-assembled [2]rotaxanes. Moreover, these binding sites can be reversibly and efficiently interconverted with their hydrazo forms through a hydrogenation dehydrogenation strategy of the nitrogen nitrogen bond. This novel chemically switchable control element has been implemented in stimuli-responsive molecular shuttles that work through a reversible azo/hydrazo interconversion, producing large amplitude net positional changes with a good discrimination between the binding sites of the macrocycle in both states of the shuttle. These molecular shuttles are able to operate by two different mechanisms: in a discrete mode through two reversible and independent chemical events and, importantly, in a continuous regime through a catalyzed ester bond formation reaction in which the shuttle acts as an organocatalyst. In this latter, the incorporation of both states of the shuttle into this simple chemical reaction network promotes a dynamic translocation of the macrocycle between two nitrogen and carbon-based stations of the thread allowing an energetically uphill esterification process to take place.
引用
收藏
页码:10741 / 10747
页数:7
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