Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747, AG, Groningen, The Netherlands.
Chemistry. 2018 Aug 27;24(48):12728-12733. doi: 10.1002/chem.201802846. Epub 2018 Jul 18.
Dehydroalanine (Dha) is a remarkably versatile non-canonical amino acid often found in antimicrobial peptides. Herein, we present the catalytic modification of Dha by a palladium-mediated cross-coupling reaction. By using Pd(EDTA)(OAc) as water-soluble catalyst, a variety of arylboronic acids was coupled to the dehydrated residues in proteins and peptides, such as Nisin. The cross-coupling reaction gave both the Heck product, in which the sp -hybridisation of the α-carbon is retained, as well as the conjugated addition product. The reaction can be performed under mild aqueous conditions, which makes this method an attractive addition to the palette of bio-orthogonal catalytic methods.
脱水氨酸 (Dha) 是一种非常通用的非典型氨基酸，通常存在于抗菌肽中。在此，我们提出了一种钯介导的交叉偶联反应对 Dha 的催化修饰。通过使用水溶性催化剂 Pd(EDTA)(OAc)，各种芳基硼酸与蛋白质和肽中的脱水残基（如乳链菌肽）偶联。该交叉偶联反应得到了 Heck 产物和共轭加成产物，其中α-碳的 sp 杂化得到保留。该反应可以在温和的水相条件下进行，这使得该方法成为生物正交催化方法的一个有吸引力的补充。
