Rotaxane formation under thermodynamic control
Rotaxane formation under thermodynamic control
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DOI：
10.1021/ol990966j
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发表时间：
1999-11-04
期刊：
影响因子：
5.2
通讯作者：
Stoddart, JF
中科院分区：
文献类型：
--
作者：
Cantrill, SJ;Rowan, SJ;Stoddart, JF
[图形]热力学控制在基于二苄基铵离子/冠醚识别基序的[2]轮烷的合成中进行，当二苯并[24]冠-8添加到含有二亚胺哑铃状组分的乙腈溶液中时，体系的动态性质(即亚胺水解/重整)使环组分能够进入NH2+中心，从而允许相应的“动态”[2]轮烷发生自组装。这种[2]轮烷的“固定”可以通过亚胺键的还原来实现，提供了一种动力学惰性的[2]轮烷。
[GRAPHICS]Thermodynamic control operates in the synthesis of a [2]rotaxane based upon the dibenzylammonium ion/crown ether recognition motif, When dibenzo[24]crown-8 is added to an acetonitrile solution containing a diimine dumbbell-like component, the dynamic nature of the system (i.e., imine hydrolysis/reformation) offers the ring component access to the NH2+ center, allowing the self-assembly of the corresponding "dynamic" [2]rotaxane to occur. The "fixing" of this [2]rotaxane can be achieved upon reduction of the imine bonds, affording a kinetically inert [2]rotaxane.