一种合成Nα-或Nω-二硫代琥珀酰基（Dts）氨基酸和二肽的简便通用方法：聚乙二醇作为功能纯化载体的应用
A convenient general method for synthesis of N alpha- or N omega-dithiasuccinoyl (Dts) amino acids and dipeptides: application of polyethylene glycol as a carrier for functional purification.
作者信息
Zalipsky S, Albericio F, Słomczyńska U, Barany G
机构信息
Department of Chemistry, University of Minnesota, Minneapolis.
出版信息
Int J Pept Protein Res. 1987 Dec;30(6):740-83. doi: 10.1111/j.1399-3011.1987.tb03386.x.
N alpha-Dithiasuccinoyl (Dts) amino acids needed for solid-phase peptide synthesis have been prepared in good yields and excellent purities by a new method that exploits the solubility properties of polyethylene glycol (PEG; bifunctional with average molecular weight 2000 was found to be optimal). Suitably side-chain protected amino acid derivatives are first reacted with a polymeric xanthate, following which the free alpha-carboxyl is blocked by silylation and the Dts heterocycle is elaborated in the same pot by reaction with chlorocarbonylsulfenyl chloride. Upon aqueous work-up, the polymeric carrier removes any urethane blocked amino acids which arise during the process. Exaggerated conditions were explored to prove the power of this functional purification approach, and mechanisms of formation of polymer-bound urethanes are proposed and supported by solution model studies. The preparation and characterization of the companion N-(iso-propyldithio)carbonyl derivative of proline is also presented.
通过一种利用聚乙二醇（PEG；发现平均分子量为2000的双功能PEG最为合适）溶解性的新方法，已以高收率和高纯度制备了固相肽合成所需的Nα-二硫代琥珀酰基（Dts）氨基酸。首先使适当侧链保护的氨基酸衍生物与聚合物黄原酸酯反应，然后通过硅烷化封闭游离的α-羧基，并在同一反应釜中通过与氯羰基硫酰氯反应来构建Dts杂环。在水相后处理过程中，聚合物载体除去了该过程中产生的任何氨基甲酸酯封端的氨基酸。探索了极端条件以证明这种功能纯化方法的有效性，并提出了聚合物结合氨基甲酸酯的形成机制，并得到溶液模型研究的支持。还介绍了脯氨酸的配套N-（异丙基二硫代）羰基衍生物的制备和表征。
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