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A facile route to old and new cyclophanes via self-assembly and capture.
Nature Communications ( IF 14.7 ) Pub Date : 2016-Apr-04 , DOI: 10.1038/ncomms11052 Mary S. Collins , Matthew E. Carnes , Bryan P. Nell , Lev N. Zakharov , Darren W. Johnson
Nature Communications ( IF 14.7 ) Pub Date : 2016-Apr-04 , DOI: 10.1038/ncomms11052 Mary S. Collins , Matthew E. Carnes , Bryan P. Nell , Lev N. Zakharov , Darren W. Johnson
Cyclophanes are a venerable class of macrocyclic and/or cage compounds that often feature high strain, unusual conformations and quite surprising properties, many of which are legendary in physical organic chemistry. However, the discovery of new, diverse cyclophanes and derivatives has been hindered by syntheses that are traditionally low-yielding, requiring long reaction times, laborious purification steps and often extreme conditions. Herein, we demonstrate a new self-assembly route to a variety of discrete cyclic and caged disulfide structures, which can then be kinetically captured upon sulfur extrusion at room temperature to give a diversity of new thioether (hetera)cyclophanes in high yield. In addition to the synthesis of novel macrocycles (dimers through hexamers), this process provides an improved route to a known macrobicyclic trithiacyclophane. This technique also enables the facile isolation of a tetrahedral macrotricyclic tetrathiacyclophane in two steps at an ambient temperature.
中文翻译:
通过自组装和捕获,轻松到达旧和新的Cyclphanes的路线。
环烷是一类古老的大环和/或笼型化合物,通常具有高应变,异常构象和令人惊讶的特性,其中许多在物理有机化学中是传奇的。然而,新的,多样的环烷及其衍生物的发现已被传统上产率低,需要较长的反应时间,费力的纯化步骤以及通常在极端条件下的合成所阻碍。在本文中,我们展示了一种新的自组装路线,可通往多种离散的环状和笼状二硫键结构,然后在室温下硫磺挤出后可以动力学捕获,从而以高收率得到各种新的硫醚(杂)环烷。除了合成新的大环化合物(二聚体到六聚体)之外,该方法提供了通往已知的大双环三硫杂环戊烷的改进途径。该技术还能够在环境温度下分两步轻松地分离四面体大三环四硫杂环丁烷。
更新日期:2016-04-07
中文翻译:
通过自组装和捕获,轻松到达旧和新的Cyclphanes的路线。
环烷是一类古老的大环和/或笼型化合物,通常具有高应变,异常构象和令人惊讶的特性,其中许多在物理有机化学中是传奇的。然而,新的,多样的环烷及其衍生物的发现已被传统上产率低,需要较长的反应时间,费力的纯化步骤以及通常在极端条件下的合成所阻碍。在本文中,我们展示了一种新的自组装路线,可通往多种离散的环状和笼状二硫键结构,然后在室温下硫磺挤出后可以动力学捕获,从而以高收率得到各种新的硫醚(杂)环烷。除了合成新的大环化合物(二聚体到六聚体)之外,该方法提供了通往已知的大双环三硫杂环戊烷的改进途径。该技术还能够在环境温度下分两步轻松地分离四面体大三环四硫杂环丁烷。