Synthesis of Nonnatural Helical Polypeptide via Asymmetric Polymerization and Reductive Cleavage of N–O Bond,Macromolecules

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Synthesis of Nonnatural Helical Polypeptide via Asymmetric Polymerization and Reductive Cleavage of N–O Bond
Macromolecules ( IF 5.1 ) Pub Date : 2017-07-14 00:00:00 , DOI: 10.1021/acs.macromol.7b01426
Yuki Ishido ₁ , Naoya Kanbayashi ₁ , Taka-aki Okamura ₁ , Kiyotaka Onitsuka ₁

Affiliation

Herein, we present a novel synthetic strategy, to amino-acid-free peptide synthesis based on postpolymerization conversion, for chiral nonnatural polypeptides. Optically active poly-N-alkoxyamides were prepared by our asymmetric polymerization as precursors of polypeptides, and the reductive cleavage of N–O bonds using a SmI₂–THF complex was carried out. The reaction proceeded smoothly with quantitative conversion to afford a nonnatural polypeptide. The resulting polypeptide adopted a one-handed stable helical structure in solution, which was established by circular dichroism (CD) and theoretical calculations using density functional theory (DFT). The simulated spectra by time-dependent (TD) DFT methods clearly indicated the validity of the proposed structure. The synthetic approach is a promising candidate for the synthesis of nonnatural polypeptides.

中文翻译：

通过不对称聚合和N-O键的还原性裂解合成非天然螺旋多肽

在这里，我们提出了一种新颖的合成策略，用于手性非天然多肽的基于聚合后转化的无氨基酸肽合成。通过我们的不对称聚合反应制备旋光性聚N-烷氧基酰胺作为多肽的前体，并使用SmI ₂还原N–O键。进行了-THF配合物。反应平稳进行并进行定量转化，得到非天然多肽。所得多肽在溶液中采用了单手稳定的螺旋结构，该结构通过圆二色性（CD）和使用密度泛函理论（DFT）的理论计算建立。通过时变（TD）DFT方法模拟的光谱清楚地表明了所提出结构的有效性。合成方法是合成非天然多肽的有前途的候选者。

更新日期：2017-07-14

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