Kondasinghe Thilini D, Saraha Hasina Y, Odeesho Samantha B, Stockdill Jennifer L
Department of Chemistry, Wayne State University, Detroit, MI 48202, USA.
Org Biomol Chem. 2017 Apr 5;15(14):2914-2918. doi: 10.1039/c7ob00536a.
The synthesis of disulfide-containing polypeptides represents a long-standing challenge in peptide chemistry, and broadly applicable methods for the construction of disulfides are in constant demand. Few strategies exist for on-resin formation of disulfides directly from their protected counterparts. We present herein a novel strategy for the on-resin construction of disulfides directly from Allocam-protected cysteines. Our palladium-mediated approach is mild and uses readily available reagents, requiring no special equipment. No reduced peptide intermediates or S-allylated products are observed, and no residual palladium can be detected in the final products. The utility of this method is demonstrated through the synthesis of the C-carboxy analog of oxytocin.
含二硫键多肽的合成是肽化学领域长期面临的挑战，人们一直需要广泛适用的二硫键构建方法。直接从其受保护的对应物在树脂上形成二硫键的策略很少。我们在此提出一种直接从Allocam保护的半胱氨酸在树脂上构建二硫键的新策略。我们的钯介导方法温和，使用容易获得的试剂，无需特殊设备。未观察到还原肽中间体或S-烯丙基化产物，并且在最终产物中未检测到残留钯。通过合成催产素的C-羧基类似物证明了该方法的实用性。
