Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9, 1060 Vienna, Austria.
J Org Chem. 2012 May 4;77(9):4432-7. doi: 10.1021/jo300219v. Epub 2012 Apr 24.
A highly selective Ru(3)(CO)(12)-catalyzed deuteration method using t-BuOD as deuterium source is reported. Electron-rich and electron-poor N-heteroarenes such as indoles, azaindoles, deazapurines, benzimidazole, quinolines, isoquinolines, and pyridines were efficiently deuterated at specific positions with high selectivity; in most cases, deuterium incorporation was close to the theoretically possible values. To further increase deuteration degrees, several cycles of the reaction protocol can be carried out which gave superior deuteration degrees employing a much lower excess of deuterating agent compared to established protocols. It was proved that the same protocol can in principle be applied to tritiation reactions important for radioactive labeling of bioactive molecules.
本文报道了一种高选择性的 Ru(3)(CO)(12)催化氘代方法，以 t-BuOD 作为氘源。富电子和缺电子的 N-杂芳环，如吲哚、氮杂吲哚、去氮嘌呤、苯并咪唑、喹啉、异喹啉和吡啶，在特定位置被高效且高选择性地氘代；在大多数情况下，氘的掺入接近理论上可能的值。为了进一步提高氘代程度，可以进行多次反应循环，与已建立的方法相比，使用更少的氘代试剂就可以得到更高的氘代程度。事实证明，该方案原则上可应用于放射性标记生物活性分子的重要的氚化反应。
