Biomimetic monoacylation of diols in water. Lanthanide-promoted reactions of methyl benzoyl phosphate
Biomimetic monoacylation of diols in water. Lanthanide-promoted reactions of methyl benzoyl phosphate
复制标题
DOI：
10.1021/ja049538l
复制
发表时间：
2004-09-01
影响因子：
15
通讯作者：
Kluger, R
中科院分区：
文献类型：
--
作者：
Cameron, LL;Wang, SC;Kluger, R
在水中通过酰基磷酸单酯直接单酰化二醇是通过氨酰基腺苷酸酯酶促氨酰化tRNA的仿生类似物。在没有催化剂的情况下，酰基磷酸单酯与胺反应迅速，但与水和醇反应非常缓慢。镧系离子显着和选择性地促进碱催化的单酰化二醇在水中由甲基苯甲酰磷酸（MBP），一个典型的酰基磷酸单酯，在中性溶液中，反应性胺质子化和非反应性。在镧系元素存在下，各种二醇与MBP的反应模式和反应性与涉及从镧系元素与二醇和MBP的双二齿络合物的共轭碱的内部加成的机制一致。该方法也适用于核苷的反应，如腺苷的2 ′-或3 ′-羟基的选择性单酰化所证明的，而5 ′-羟基或6-氨基没有反应。没有二醇的腺苷类似物是不反应的。这表明该方法将选择性地单酰化形成3 '末端的tRNA中独特二醇处的羟基。
The direct monoacylation of diols by acyl phosphate monoesters in water is a biomimetic analogy to the enzymic aminoacylation of tRNA by aminoacyl adenylates. Without catalysis, acyl phosphate monoesters react rapidly with amines but very slowly with water and alcohols. Lanthanide ions dramatically and selectively facilitate the base-catalyzed monoacylation of diols in water by methyl benzoyl phosphate (MBP), a typical acyl phosphate monoester, in neutral solutions where reactive amines are protonated and unreactive. The reaction patterns and reactivity of various diols with MBP in the presence of lanthanides are consistent with a mechanism that involves internal addition from the conjugate base of the bis-bidentate complex of the lanthanide with the diol and MBP. The method is also applicable to reactions of nucleosides as evidenced by the selective monoacylation of the 2'- or 3'-hydroxyl group of adenosine, without reaction of the 5'-hydroxyl group or the 6-amino group. Analogues of adenosine without the diol are unreactive. This suggests that the method will selectively monoacylate the hydroxyl groups at the unique diol in tRNA that forms the 3'-terminus.