Botha F, Böhm S, Dvořáková H, Eigner V, Lhoták P
Department of Organic Chemistry, Institute of Chemical Technology, Prague (ICTP), Technicka 6, 166 28 Prague 6, Czech Republic.
Org Biomol Chem. 2014 Jul 28;12(28):5136-43. doi: 10.1039/c4ob00799a.
The first mercuration in the thiacalixarene series using thiacalix[4]arenes immobilized in the cone or 1,3-alternate conformations gave a mixture of two monomercurated regioisomers (meta and para) in approx. 4 : 1 and 2 : 1 ratios, respectively. The organomercurial intermediates show unusual solid-state behaviour, as evidenced by the formation of η(6) complexes, and can be easily transformed into halogen-substituted derivatives, so far inaccessible in thiacalixarene chemistry. This paves the way towards the synthesis of inherently chiral thiacalixarene-based receptors with an unusual substitution pattern.
在硫杂杯芳烃系列中，首次使用固定在锥形或1,3-交替构象中的硫杂杯[4]芳烃进行汞化反应，分别以约4∶1和2∶1的比例得到了两种单汞化区域异构体（间位和对位）的混合物。有机汞中间体表现出不同寻常的固态行为，这可通过η(6)配合物的形成得到证明，并且可以很容易地转化为卤代衍生物，这在硫杂杯芳烃化学中迄今为止是无法实现的。这为合成具有不寻常取代模式的固有手性硫杂杯芳烃基受体铺平了道路。
