Department of Chemistry, Biochemistry and Materials Science Institute, University of Oregon, Eugene, OR 97403-1253, USA.
Instituto de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, Ciudad de México, 04510, México.
Chempluschem. 2020 Jun;85(6):1270-1282. doi: 10.1002/cplu.202000257.
Dynamic Covalent Chemistry (DCC) - combining the robustness of covalent bonds with the self-correcting nature of supramolecular chemistry - facilitates the modular synthesis of complex molecular assemblies in high yields. Although numerous reactions form covalent bonds, only a small set of chemical transformations affect covalent bond formation reversibly under suitable conditions for DCC. Further progress in this area still requires the identification of dynamic motifs and greater insights into their reversibility. We have fruitfully employed DCC of both thiolate coordination to main-group elements and disulfide formation for the facile self-assembly of: (1) metal/metalloid-thiolate assemblies, and (2) purely organic cyclic and caged disulfides, thioethers, and even hydrocarbons, many of which have remained elusive by traditional stepwise synthesis yet form readily through our methods. In this Minireview, we highlight the approaches to prepare these unusual compounds and the factors inducing structural transformations or favoring the formation of certain products over others, given a set of external stimuli or reaction conditions.
动态共价化学（DCC）——将共价键的坚固性与超分子化学的自我修正性质相结合——促进了复杂分子组装体的模块化合成，产率高。尽管许多反应形成共价键，但只有一小部分化学转化在适合 DCC 的条件下可逆地影响共价键的形成。在这一领域的进一步进展仍然需要识别动态基元和对其可逆性的更深入了解。我们已经成功地将硫醇配位与主族元素的 DCC 以及二硫化物的形成用于：（1）金属/类金属-硫醇组装体，和（2）纯有机环状和笼状二硫化物、硫醚，甚至烃类的简便自组装，其中许多通过传统的逐步合成仍然难以捉摸，但通过我们的方法很容易形成。在这篇综述中，我们强调了制备这些不寻常化合物的方法，以及在给定一组外部刺激或反应条件下，诱导结构转变或有利于形成某些产物而不是其他产物的因素。
