炔烃的分子内反膦金化反应：一种基于FLP原理合成稳定金化磷吲哚鎓配合物的方法。
Intramolecular anti-Phosphinoauration of Alkynes: An FLP-Motivated Approach to Stable Aurated Phosphindolium Complexes.
作者信息
Arndt Sebastian, Hansmann Max M, Motloch Petr, Rudolph Matthias, Rominger Frank, Hashmi A Stephen K
机构信息
Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Chemistry Department, Faculty of Science, King Abdulaziz University (KAU), Jeddah, 21589, Saudi Arabia.
出版信息
Chemistry. 2017 Feb 21;23(11):2542-2547. doi: 10.1002/chem.201605914. Epub 2017 Feb 3.
The synthesis of aurated phosphindolium complexes from easy accessible 1,5-alkynylphosphine derivatives has been studied by using gold(I) complexes featuring carbene and phosphine ligands as initiators. Upon formation of the mixed phosphine NHC/phosphine gold species, elevated temperatures induced the cyclization to give stable aurated phosphindolium salts, which is supported by DFT calculations. The key elementary step that comprises a yet unknown anti-phosphinoauration of an unactivated alkyne is favored if bulky NHC ligands are used which was analyzed by kinetic measurements. This concept could furthermore be extended to neutral (phosphindolium)AuCl complexes featuring the yet unknown phosphindole ligand.
利用具有卡宾和膦配体的金（I）配合物作为引发剂，研究了由易于获得的1,5-炔基膦衍生物合成金化磷吲哚鎓配合物的反应。在形成混合膦NHC/膦金物种后，升高温度会引发环化反应，生成稳定的金化磷吲哚鎓盐，这得到了密度泛函理论计算的支持。动力学测量分析表明，如果使用庞大的NHC配体，包含未活化炔烃的未知反膦金化反应的关键基元步骤会更有利。此外，这一概念还可扩展到具有未知膦吲哚配体的中性（磷吲哚鎓）AuCl配合物。
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