N-Phosphorylated Imidazolium Salts as Precursors to 2- and 5-Phosphorylated Imidazoles and New Imidazol-2-ylidenes Featuring the PNCN Unit
作者:Anatolii P. Marchenko、Heorgii N. Koidan、Anastasiya N. Huryeva、Evgeniy V. Zarudnitskii、Aleksandr A. Yurchenko、Aleksandr N. Kostyuk
DOI:10.1021/jo101177h
日期:2010.11.5
It has been experimentally proven that the reaction of 1- or 1,2-disubstituted imidazoles with diorganylphosphorus(III) halides proceeds via initial formation of N-phosporylated imidazolium salts. Treatment of these salts with strong bases results in phosphorylation of the parent imidazoles at the 2- or 5-positions, correspondingly. In a previous case, imidazol-2-ylidenes are formed as intermediates
实验已经证明1-或1,2-二取代的咪唑与二有机基磷(III)卤化物的反应是通过最初形成N-磷酸化的咪唑鎓盐而进行的。用强碱处理这些盐会相应地导致母体咪唑在2或5位发生磷酸化。在先前的情况下,形成咪唑-2-亚基作为中间体。在N1和N3原子上都带有空间要求或/和π供体基团的情况下,将1,3-二取代的咪唑鎓盐与NaN(SiMe 3)2进行去质子化反应可得到新的稳定的N-磷取代的Arduengo型卡宾。