COMU: A Safer and More Effective Replacement for Benzotriazole-Based Uronium Coupling Reagents
COMU: A Safer and More Effective Replacement for Benzotriazole-Based Uronium Coupling Reagents
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DOI：
10.1002/chem.200900615
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发表时间：
2009-01-01
影响因子：
4.3
通讯作者：
Albericio, Fernando
中科院分区：
文献类型：
--
作者：
El-Faham, Ayman;Subiros Funosas, Ramon;Albericio, Fernando
我们描述了一个新的家庭的uronium型偶联剂，不同的亚胺部分和离去基团。与肟衍生物，特别是乙基2-氰基-2-（羟基亚氨基）乙酸酯（Oxyma）的吗啉基团的存在下，对试剂的溶解度，稳定性和反应性有显着的影响。最后，衍生自Oxyma（COMU）的新脲鎓盐在仅1当量碱的存在下表现非常好，从而证实了氢键受体在反应中的作用。COMU还显示出比基于苯并三唑的HDMA和HDMB更低的危险安全性，其表现出不可预测的自催化分解。此外，COMU中含有的Oxyma部分表明爆炸风险低于苯并三唑衍生物的情况。
We describe a new family of uronium-type coupling reagents that differ in their iminium moieties and leaving groups. The presence of the morpholino group in conjunction with an oxime derivative-especially ethyl 2-cyano-2-(hydroxyimino)acetate (Oxyma)-had a marked influence on the solubilities, stabilities, and reactivities of the reagents. Finally, the new uronium salt derived from Oxyma (COMU) performed extremely well in the presence of only 1 equiv of base, thereby confirming the effect of the hydrogen bond acceptor in the reaction. COMU also showed a less hazardous safety profile than the benzotriazole-based HDMA and HDMB, which exhibited unpredictable autocatalytic decompositions. Furthermore, the Oxyma moiety contained in COMU suggests a lower risk of explosion than in the case of the benzotriazole derivatives.