Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, United States.
Bioorg Med Chem Lett. 2011 Sep 1;21(17):5050-3. doi: 10.1016/j.bmcl.2011.04.061. Epub 2011 Apr 22.
N-Methylimidazolium chloride is found to catalyze a coupling reaction between monophosphates and activated phosphorous-nitrogen intermediates such as a phosphorimidazolide and phosphoromorpholidate to form biologically important unsymmetrical pyrophosphate diesters. The catalyst is much more active, cheaper, and less explosive than 1H-tetrazole, known as the best catalyst for the pyrophosphate formation over a decade. The mild and neutral reaction conditions are compatible with allylic pyrophosphate formation in Lipid I syntheisis. (31)P NMR experiments suggest that the catalyst acts not only as an acid but also as a nucleophile to form cationic and electrophilic phosphor-N-methylimidazolide intermediates in the pyrophosphate formation.
氯化 1-甲基咪唑被发现可以催化单磷酸酯与活化的磷-氮中间体（如磷酰亚咪唑和磷酰胺）之间的偶联反应，从而形成具有重要生物学意义的不对称焦磷酸二酯。与 1H-四唑（十多年来被认为是焦磷酸形成的最佳催化剂）相比，该催化剂的活性更高、价格更便宜、爆炸风险更小。温和中性的反应条件与脂 I 合成中的烯丙基焦磷酸形成兼容。（31）P NMR 实验表明，该催化剂不仅起酸的作用，而且在焦磷酸形成过程中还作为亲核试剂形成阳离子和亲电磷酰-N-甲基咪唑中间体。
