Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany.
Bioorg Med Chem. 2010 Jun 1;18(11):3679-86. doi: 10.1016/j.bmc.2010.04.015. Epub 2010 Apr 9.
The traceless Staudinger ligation has recently found various applications in the field of peptide synthesis and modification, including immobilization and cyclization strategies. In this report, we utilize the traceless Staudinger ligation in the formation of amide bonds, which allows the acquisition of acylated aminosugars and peptides as well as the cyclization of peptides. A key element in these synthetic procedures is the use of a borane-protected phosphinomethanethiol, which is demonstrated to be prone towards oxidation in its unprotected form, during the synthesis of phosphinothioesters. In combination with acidic and basic deprotection strategies for the borane-protected phosphinothioesters, amide bonds can be formed in the presence of azides in moderate to good overall yields.
无痕迹 Staudinger 连接最近在肽合成和修饰领域得到了广泛的应用，包括固定化和环化策略。在本报告中，我们在酰胺键的形成中利用无痕迹 Staudinger 连接，从而获得酰化的氨基糖和肽以及肽的环化。这些合成步骤的一个关键要素是使用硼烷保护的膦基甲硫醇，其在未保护的形式下易于在合成膦硫酯时被氧化。与硼烷保护的膦硫酯的酸性和碱性脱保护策略相结合，酰胺键可以在叠氮化物的存在下以中等至良好的总收率形成。
