N-Methylimidazolium chloride-catalyzed pyrophosphate formation: Application to the synthesis of Lipid I and NDP-sugar donors

BIOORGANIC & MEDICINAL CHEMISTRY LETTERS

卷:21

Article

Tsukamoto, Hirokazu¹  Kahne, Daniel¹ 

[1] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA

关键词: N-Methylimidazolium chloride;    Pyrophosphate formation;    Phosphorimidazolide;    Phosphoromorpholidate;    Lipid I;    NDP-sugar donors;   

DOI  :  10.1016/j.bmcl.2011.04.061

来源: Elsevier

【 摘 要 】

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. (c) 2011 Elsevier Ltd. All rights reserved.

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