Assembly of Water-Soluble, Dynamic, Covalent Container Molecules and Their Application in the Room-Temperature Stabilization of Protoadamantene
Assembly of Water-Soluble, Dynamic, Covalent Container Molecules and Their Application in the Room-Temperature Stabilization of Protoadamantene
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DOI：
10.1002/chem.201200602
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发表时间：
2012-10-01
影响因子：
4.3
通讯作者：
Warmuth, Ralf
中科院分区：
文献类型：
--
作者：
Lin, Zhihua;Sun, Junling;Warmuth, Ralf
在合适的模板客体存在下，水溶性四甲酰空腔体和2与两个等量的H-2(CH2)(n)NH2 （n=2-4）的热力学控制反应得到半复合物1a-e。来宾，其产量取决于来宾的大小和形状之间的匹配和内相。这些半复合物是动态的，在加酸时解离，在碱化时重新形成。在水中，它们通过亚胺键的暂时水解来交换客体。以1b为分子反应瓶，包封3-去甲金刚烷基重氮吡啶6，在350 nm处以4:1的比例进行光解，得到Bredt烯烃原金刚烷5和1-去甲金刚烷基重氮甲烷8。包封的原金刚烯在室温下（CD3）(2)SO/CD3CN （t(1/2)=5.5天）稳定，在D2O中的寿命为几分钟。
The thermodynamically controlled reactions of water-soluble tetra-formylcavitand 2 with two equivalents of H-2(CH2)(n)NH2 (n=2-4) in the presence of a suitable templating guest give hemicarceplexes 1a-e.guest, the yield of which depends on the match between size and shape of the guest and that of the inner phase. These hemicarceplexes are dynamic and dissociate upon addition of acid and reform upon basification. In water, they exchange guests through temporary hydrolysis of imine bonds. To test 1b as molecular reaction flask, 3-noradamantyldiazirine 6 was encapsulated and photolyzed at 350 nm to produce Bredt olefin protoadamantene 5 and 1-noradamantyldiazomethane 8 in a 4:1 ratio. Encapsulated protoadamantene is stable for days at room temperature in (CD3)(2)SO/CD3CN (t(1/2)=5.5 days) and has a lifetime of several minutes in D2O.