Wurm Thomas, Hornung Julius, O'Neill Matthew, Rudolph Matthias, Rominger Frank, Hashmi A Stephen K
Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah, 21589, Saudi Arabia.
Chemistry. 2017 Apr 11;23(21):5143-5147. doi: 10.1002/chem.201700214. Epub 2017 Mar 27.
Starting from DMSAuCl, isonitriles and functionalized propargylammonium salts in the presence of simple trimethylamine as auxiliary base, unsymmetrically substituted ester- and phosphonate-functionalized Au -imidazolylidene complexes were synthesized in an easy-to-use modular one-pot template synthesis. In the course of the reaction, after the initial nucleophilic addition of the amine to the gold(I)-activated isonitrile, a Michael addition closes the N-heterocyclic carbene (NHC) ring. Then the remaining double bond migrates into the NHC ring, evidently a more stable position than the initial exocyclic double bond. These functional groups attached to the back bone of the NHC ligands represent ideal handles for a further modification of the system, for example an attachment to larger assemblies or heterogenization by an attachment to surfaces are conceivable.
从二甲基硫代金（I）氯出发，在简单的三甲胺作为辅助碱的存在下，异腈和官能化炔丙基铵盐反应，通过易于操作的模块化一锅模板合成法制备了不对称取代的酯基和膦酸酯基官能化的金-咪唑亚基配合物。在反应过程中，胺首先对金（I）活化的异腈进行亲核加成，随后迈克尔加成反应闭合N-杂环卡宾（NHC）环。然后，剩余的双键迁移至NHC环内，显然这是一个比初始环外双键更稳定的位置。这些连接在NHC配体主链上的官能团是对该体系进行进一步修饰的理想基团，例如，可以设想将其连接到更大的组装体上，或者通过连接到表面实现多相化。
