Synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and spermidines. Elucidation of the stereochemical course of putrescine aminopropyltransferase (spermidine synthase)
Synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and spermidines. Elucidation of the stereochemical course of putrescine aminopropyltransferase (spermidine synthase)
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手性氘代（S-腺苷-S-甲基磺酰基）丙胺和亚精胺的合成。
DOI：
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发表时间：
1988
期刊：
影响因子：
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通讯作者：
J. Coward
中科院分区：
文献类型：
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作者：
G. R. Orr;D. Danz;G. Pontoni;P. Prabhakaran;S. Gould;J. Coward
研究了酶催化氨丙基转移反应的立体化学过程。手性氘代（S-腺苷-S-甲砜基）丙胺和几种手性氘代亚精胺（-）-樟脑酰胺衍生物的立体专一性合成允许通过使用/sup 1/H NMR技术阐明氨丙基转移酶立体化学。分离自大肠杆菌的腐胺氨丙基转移酶（亚精胺合酶）催化由1，4-二氨基丁烷（腐胺）和手性氘代（S-腺苷-S-甲砜基）丙胺合成手性氘代亚精胺。将生物合成的亚精胺衍生为1，8-双（Boc）亚精胺（-）-樟脑酰胺，并将它们的1HNMR谱与合成标准品的1HNMR谱进行比较，可以确定生物合成产物的绝对构型。结果表明，E.大肠杆菌亚精胺合酶在亚甲基碳上进行构型反转，受到腐胺的亲核攻击。这些数据支持通过酶和两种底物的三元复合物进行的单置换机制。参考文献42篇，附图5幅。
The stereochemical course of enzyme-catalyzed aminopropyl transfer has been investigated. The stereospecific synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and several chirally deuteriated spermidine (-)-camphanamide derivatives has allowed the elucidation of aminopropyltransferase stereochemistry by using /sup 1/H NMR techniques. Putrescine aminopropyltransferase (spermidine synthase) isolated from Eschierchia coli catalyzed the synthesis of chirally deuteriated spermidines from 1,4-diaminobutane (putrescine) and chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines. Derivatization of the biosynthetic spermidines to 1,8-bis(Boc)spermidine (-)-camphanamides and comparison of their /sup 1/H NMR spectra with those of the synthetic standards permits determination of the absolute configuration of the biosynthetic products. The results show that the reaction catalyzed by E. coli spermidine synthase proceeds with inversion of configuration at the methylene carbon undergoing nucleophilic attack by putrescine. These data support a single-displacement mechanism proceeding via a ternary complex of enzyme and both substrates. 42 references, 5 figures.