Expanding the Scope of Pnictogen‐Assisted Cyclophane Self‐Assembly
Expanding the Scope of Pnictogen‐Assisted Cyclophane Self‐Assembly
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扩大 Pnictogen 的范围——辅助环芳自组装
DOI：
10.1002/ejoc.202200056
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发表时间：
2022
影响因子：
2.8
通讯作者：
Johnson, Darren W.
中科院分区：
文献类型：
--
作者：
Shear, Trevor A.;Mayhugh, Jacob T.;Zocchi, Luca J.;Demachkie, Isabella S.;Trubenstein, Henry J.;Zakharov, Lev N.;Johnson, Darren W.
环烷是一种非常有趣的化合物，具有广泛的独特和新出现的性质。然而，合成复杂的和/或功能化的环番通常会受到反应条件苛刻，反应时间长，有时收率低的影响。我们之前报道了一种高效、高产、类金属定向的自组装方法，用于制备以巯基甲基芳烃为起始材料的二硫、硫醚和碳氢环烷和笼。在此，我们报道了21个新的二硫和硫醚组装体的合成，将这种高产的自组装方法扩展到具有多种结构的大环和笼。值得注意的是，利用电子缺陷、杂芳基、环烷基、螺基、甚至短烯基/炔基底物，在动态共价控制下，高产、高效的合成仍在进行。
Cyclophanes are a fundamentally interesting class of compounds that host a wide range of unique and emergent properties. However, synthesis of complex and/or functionalized cyclophanes can often suffer from harsh reaction conditions, long reaction times, and sometimes low yields using stepwise methods. We have previously reported an efficient, high‐yielding, metalloid‐directed self‐assembly method to prepare disulfide, thioether, and hydrocarbon cyclophanes and cages that feature mercaptomethyl‐arenes as starting materials. Herein, we report the synthesis of 21 new disulfide and thioether assemblies that expand this high yielding self‐assembly method to a wide breadth of macrocycles and cages with diverse structures. Remarkably, the high‐yielding, efficient syntheses still proceed under dynamic covalent control using electron‐deficient, heteroaryl, cycloalkyl, spiro, and even short alkenyl/alkynyl substrates.