Acceleration of a Diels-Alder reaction by a self-assembled molecular capsule
Acceleration of a Diels-Alder reaction by a self-assembled molecular capsule
复制标题
DOI：
10.1038/385050a0
复制
发表时间：
1997-01-02
期刊：
影响因子：
64.8
通讯作者：
Rebek, J
中科院分区：
文献类型：
--
作者：
Kang, JM;Rebek, J
笼状分子的内部可以被认为提供了一种新的物质相（1，2），在其中可以稳定反应中间体（3）并观察到新的立体异构形式（4）。通过弱分子间力自组装的笼状分子复合物是动态物质（5，6），可逆地包封客体分子。它们可以持续数微秒到数小时的时间，足以在其中发生化学过程。在这里，我们报告了加速狄尔斯-阿尔德反应bg封装的反应物在一个自组装分子胶囊（7，8）。虽然产品抑制（缺乏解离）防止系统显示真正的催化行为，有明显的证据表明，由于胶囊内的浓度的有效增强，速率增加了两个数量级以上。
THE interior of cage-like molecules can be considered to provide a new phase of matter(1,2), in which it becomes possible to stabilize reactive intermediates(3) and to observe new forms of stereoisomerism(4). Cage-like molecular complexes that self-assemble through weak intermolecular forces are dynamic species(5,6), encapsulating guest molecules reversibly. They can persist over timescales ranging from microseconds to hours, long enough for chemical processes to take place within them. Here we report the acceleration of a Diels-Alder reaction bg encapsulation of the reactants in a self-assembling molecular capsule(7,8). Although product inhibition (lack of dissociation) prevents the system from showing true catalytic behaviour, there is clear evidence for a rate increase of over two orders of magnitude owing to the effective enhancement of concentration inside the capsule.