SYNTHESIS OF QUEUINE, THE BASE OF NATURALLY-OCCURRING HYPERMODIFIED NUCLEOSIDE (QUEUOSINE), AND ITS ANALOGS
SYNTHESIS OF QUEUINE, THE BASE OF NATURALLY-OCCURRING HYPERMODIFIED NUCLEOSIDE (QUEUOSINE), AND ITS ANALOGS
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DOI：
10.1039/p19880001637
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发表时间：
1988-07-01
期刊：
影响因子：
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通讯作者：
NISHIMURA, S
中科院分区：
文献类型：
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作者：
AKIMOTO, H;IMAMIYA, E;NISHIMURA, S
一种合成queuine (1) {2-氨基-5-[(1S,2R,3S)-2,3-二羟基环戊-4-烯基氨基甲基]吡咯并[2,3-d]嘧啶-4(3H)-one}的便捷新方法，queuine是存在于某些转移RNA中的天然存在的超修饰核苷queuosine的基础，及其生物合成前体， 2-氨基-5-氨基甲基吡咯并[2,3-d]嘧啶-4(3H)-酮(2)（Pre Q1碱基）被成功开发。该方法涉及两个关键反应：使用 2-酰氨基吡咯并[2,3-d]嘧啶-4(3H)-one (7) 的二苄氨基甲醛的曼尼希反应，导致将二苄氨基甲基选择性引入 (7) 的 5-位，以及所得曼尼希碱 (17) 中 5-二苄氨基官能团的胺交换反应(1S,2R,3S)-2,3-异亚丙基二氧基环戊-4-烯胺，得到所需的队列(1)。 (17) 与氨发生类似反应，得到奎因 (2)（Pre Q1 碱）的生物合成前体。因此，通过(17)与适当的胺的胺交换反应或通过(2)与适当的酰化剂的酰化，合成了一系列在其5-氨基甲基侧链中具有结构变化的队列类似物。
A convenient new method for synthesizing queuine (1) {2-amino-5-[(1S,2R,3S)-2,3-dihydroxycyclopent-4-enylaminomethyl]pyrrolo[2,3-d]pyrimidin-4(3H)-one}, the base of the naturally occurring hypermodified nucleoside, queuosine, present in certain transfer RNAs, and its biosynthetic precursor, 2-amino-5-aminomethylpyrrolo[2,3-d]pyrimidin-4(3H)-one (2) (Pre Q1 base), was successfully exploited. This method involved two critical reactions: the Mannich reaction using dibenzylamino-formaldehyde of 2-acylaminopyrrolo[2,3-d]pyrimidine-4(3H)-one (7), which resulted in the selective introduction of the dibenzylaminomethyl group into the 5-position of (7), and an amine exchange reaction of the 5-dibenzylamino function in the resulting Mannich base (17) with (1S,2R,3S)-2,3-isopropylidenedioxycyclopent-4-enylamine, which yielded the desired queuine (1). Similar reaction of (17) with ammonia gave the biosynthetic precursor of queuine (2) (Pre Q1 base). Thus, a series of queuine analogues with structural variations in their 5-aminomethyl side-chains was synthesized by the amine exchange reaction of (17) with appropriate amines or by acylation of (2) with appropriate acylating agents.