Abstract：
While remarkable progress has been made in the development of peptide medicines, many problems related to peptide synthesis remain unresolved. Previously, we reported electrochemical peptide synthesis using a phosphine as a potentially recyclable coupling reagent. However, there was room for improvement from the point of view of reaction efficiency, especially in the carboxylic acid activation step and the peptide bond formation step. To overcome these challenges, we searched for the optimal phosphine. Among phosphines with various electronic properties, we found that electron-rich triaryl phosphines improved the reaction efficiency. Consequently, we successfully performed electrochemical peptide synthesis on sterically hindered and valuable amino acids. We also synthesized oligopeptides that were challenging with our previous method. Finally, we examined the effect of substituents on the phosphine cations, and gained some insights into reactivity, which will aid researchers designing reactions involving phosphine cations.
摘要：
虽然多肽药物的开发取得了显著进展，与肽合成相关的许多问题仍未解决。以前,我们报道了使用膦作为潜在可回收的偶联剂的电化学肽合成。然而,从反应效率的角度来看，还有改进的空间，特别是在羧酸活化步骤和肽键形成步骤中。为了克服这些挑战，我们寻找最佳的磷化氢。在具有各种电子性质的膦中，我们发现富电子三芳基膦提高了反应效率。因此,我们成功地在空间位阻和有价值的氨基酸上进行电化学肽合成。我们还合成了我们以前的方法具有挑战性的寡肽。最后,我们研究了取代基对膦阳离子的影响，并获得了一些反应性的见解，这将有助于研究人员设计涉及膦阳离子的反应。
