Key Laboratory of Preclinical Study for New Drugs of Gansu Province, School of Basic Medical Science, Lanzhou University, Lanzhou, 730000, China.
Institute of Biochemistry and Molecular Biology, School of Life Sciences, Lanzhou University, Lanzhou, 730000, China.
Nat Commun. 2021 Nov 25;12(1):6873. doi: 10.1038/s41467-021-27086-x.
The visible light induced, photocatalysts or photoabsorbing EDA complexes mediated cleavage of pyridinium C-N bond were reported in the past years. Here, we report an ionic compound promote homolytic cleavage of pyridinium C-N bond by exploiting the photonic energy from visible light. This finding is successfully applied in deaminative hydroalkylation of a series of alkenes including naturally occurring dehydroalanine, which provides an efficient way to prepare β-alkyl substituted unnatural amino acids under mild and photocatalyst-free conditions. Importantly, by using this protocol, the deaminative cyclization of peptide backbone N-terminals is realized. Furthermore, the use of EtN or PPh as reductants and HO as hydrogen atom source is a practical advantage. We anticipate that our protocol will be useful in peptide synthesis and modern peptide drug discovery.
过去几年中，已有研究报道了可见光诱导的光催化剂或光吸收 EDA 配合物介导的吡啶鎓 C-N 键的断裂。在这里，我们报告了一种离子化合物，通过利用可见光的光子能量，促进吡啶鎓 C-N 键的均裂断裂。这一发现成功地应用于一系列烯烃的脱氨氢烷基化反应中，包括天然存在的脱氢丙氨酸，这为在温和无催化剂条件下制备β-烷基取代的非天然氨基酸提供了一种有效方法。重要的是，通过使用该方案，可以实现肽骨架 N 端的脱氨环化。此外，使用 EtN 或 PPh 作为还原剂和 HO 作为氢原子源是一个实际的优势。我们预计我们的方案将在肽合成和现代肽药物发现中有用。
