Oxidative acylation using thioacids
Oxidative acylation using thioacids
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DOI：
10.1038/37944
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发表时间：
1997-09-04
期刊：
影响因子：
64.8
通讯作者：
Orgel, LE
中科院分区：
文献类型：
--
作者：
Liu, RH;Orgel, LE
一些重要的益生元反应，包括通过形成酰胺键将氨基酸偶联成多肽，都涉及酰化。这些反应对理解益生元合成提出了挑战。依靠脱水剂的缩合反应要么在水溶液中效率低下（1,2），要么需要强酸性条件和高温(3)。因此，巯基酯衍生物等活化氨基酸被认为可能是益生元肽合成的底物（4-7）。在这里，我们提出了一个密切相关的途径，酰胺键形成涉及氧化酰化的硫代酸。我们发现苯丙氨酸、亮氨酸和苯磷酸酯在硫乙酸和氧化剂的作用下能在水溶液中有效地酰化，从益生元的角度来看，氧化酰化具有在溶液和温和条件下高效进行的优点。我们预计氧化酰化应该被证明是激活羧酸，包括氨基酸的一般方法。
Several important prebiotic reactions, including the coupling of amino acids into polypeptides by the formation of amide linkages, involve acylation. Theae reactions present a challenge to the understanding of prebiotic synthesis. Condensation reactions relying on dehydrating agents are either inefficient in aqueous solution(1,2) or require strongly acidic conditions and high temperatures(3). Activated amino acids such as thioester derivatives have therefore been suggested as likely substrates for prebiotic peptide synthesis(4-7). Here we propose a closely related route to amide bond formation involving oxidative acylation by thioacids. We find that phenylalanine, leucine and phenylphosphate are acylated efficiently in aqueous solution by thioacetic acid and oxidizing agent, From a prebiotic point of view, oxidative acylation has the advantage of proceeding efficiently in solution and under mild conditions. We anticipate that oxidative acylation should prove to be a general method for activating carboxylic acids, including amino acids.