Institute for Integrated Cell-Material Sciences, Kyoto University Institute for Advanced Study, Kyoto University, Yoshida Ushinomiyacho, Sakyo-ku, Kyoto 606-8501, Japan.
Chem Commun (Camb). 2018 May 8;54(38):4782-4785. doi: 10.1039/c8cc01837e.
Kinetic stabilisation of unstable chemical species in nanospace is of potential importance in the field of materials and synthetic chemistry, and porous coordination polymers (PCPs) represent a facile platform to provide such reaction fields. Thiyl radicals are important reactive substances that often play a leading role in organic and bioorganic chemistry. However, their generation in nanospace has been barely investigated due to synthetic difficulties. Here, we report a facile methodology for the functionalisation of active thiyl substituents on PCP pore surfaces using a post-synthetic protection and deprotection technique. The thiyl radicals were generated inside a zinc(ii)-based PCP upon the deprotection of asymmetric disulfides, which were used as the protecting groups by ultraviolet light irradiation.
纳米空间中不稳定化学物质的动力学稳定化在材料和合成化学领域具有重要意义，而多孔配位聚合物 (PCP) 则为提供这种反应场提供了一个简单的平台。硫自由基是重要的反应性物质，它们在有机和生物有机化学中经常起主导作用。然而，由于合成困难，它们在纳米空间中的生成几乎没有被研究过。在这里，我们报告了一种使用后合成保护和去保护技术在 PCP 孔表面上功能化活性硫自由基的简便方法。硫自由基是在锌 (ii) 基 PCP 内部通过不对称二硫的去保护生成的，它们被紫外线照射用作保护基团。
