Pal Sunit, 't Hart Peter
Chemical Genomics Centre, Max Planck Institute of Molecular Physiology, Dortmund, Germany.
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, United States.
Methods Mol Biol. 2025;2934:137-146. doi: 10.1007/978-1-0716-4578-9_10.
Late-stage functionalization of specific residues in a peptide provides a fast and straightforward method to unnatural amino acids. Here we provide a protocol for the photochemical conversion of redox-active esters formed from aspartic acid and glutamic acid. The reaction involves the formation of an electron-donor acceptor complex using the Hantzsch ester, which leads to radical decarboxylation under irradiation with purple light. The formed carbon radical then adds to a Nickel aryl bromide complex to facilitate C-C cross coupling. By using widely available aryl bromides a broad scope of unnatural aromatic amino acids can be accessed. Since all steps take place on solid support, the protocol is rapid and easy to perform.
肽中特定残基的后期功能化提供了一种快速且直接的引入非天然氨基酸的方法。在此，我们提供了一种由天冬氨酸和谷氨酸形成的氧化还原活性酯的光化学转化方案。该反应涉及使用汉斯酯形成电子供体 - 受体复合物，在紫光照射下导致自由基脱羧。然后形成的碳自由基加成到镍芳基溴络合物上以促进碳 - 碳交叉偶联。通过使用广泛可得的芳基溴化物，可以获得多种非天然芳香族氨基酸。由于所有步骤都在固相载体上进行，该方案快速且易于操作。
