Regioselective α-Peptide Bond Formation Through the Oxidation of Amino Thioacids
Regioselective α-Peptide Bond Formation Through the Oxidation of Amino Thioacids
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通过氨基硫代酸的氧化形成区域选择性 α-肽键
DOI：
10.1021/acs.biochem.8b01239
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发表时间：
2019
期刊：
影响因子：
2.9
通讯作者：
Kajihara Yasuhiro
中科院分区：
文献类型：
--
作者：
Okamoto Ryo;Haraguchi Takuya;Nomura Kota;Maki Yuta;Izumi Masayuki;Kajihara Yasuhiro
生物系统，包括核糖体和酶，以极高的速度和准确性产生多肽。另一方面，在化学合成中，在没有保护基团的情况下，很难实现合理的、区域选择性的α-肽键的形成。在本研究中，利用α-氨基硫酸在不使用任何保护基团的情况下生成多肽。我们发现α-氨基硫酸可以氧化形成二氨基酰基-二硫键，然后进行分子内S-TON-酰基转移，形成α-肽键。即使是硫代形式的赖氨酸，它有一个自由的ε-氨基，也产生了一个区域选择性的α-肽键。氨基酸的氧化生成了氨基酸的低聚体。有趣的是，这种齐聚反应即使在铁这一益生元素的存在下也能进行，从而暗示了一种可能的益生多肽键的形成反应。
Biological systems, including ribosomes and enzymes, produce peptides with an extraordinary high speed and accuracy. On the other hand, a rational and regioselective α-peptide bond formation, without involving protecting groups, is difficult to achieve in chemical synthesis. In this study, α-amino thioacids were utilized for the generation of polypeptides without using any protecting groups. We found that an α-amino thioacid could oxidatively form a diaminoacyl-disulfide moiety and undergo a subsequent intramolecularS- toN-acyl transfer to form an α-peptide bond. Even the thioacid form of lysine, which has a free ε-amino group, generated a regioselective α-peptide bond. The oxidation of amino thioacids generated the oligomers of amino acids. Interestingly, this oligomerization reaction proceeded even in the presence of iron ore, a prebiotic element, thus suggesting a plausible prebiotic peptide bond forming reaction.