Trinuclear gold-catalyzed site-selective alkylation of peptides
作者机构：State Key Laboratory of Coordination Chemistry Jiangsu Key Laboratory of Advanced Organic Materials Chemistry and Biomedicine Innovation Center (Chem BIC) School of Chemistry and Chemical Engineering Nanjing University Green Catalysis Center College of Chemistry Zhengzhou University State Key Laboratory of Natural Medicines China Pharmaceutical University
出 版 物：《Science China Chemistry》 (中国科学:化学(英文版))
年 卷 期：2025年第01期
页 面：249-256页
核心收录：
学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学]
基 金：the National Key Research and Development Program of China (2021YFC2101900, 2022YFA1503200) the National Natural Science Foundation of China (22122103, 22101130,22001117, 22471121, 22271144) the Fundamental Research Funds for the Central Universities (020514380327) the open project of state key laboratory of natural medicines (SKLNMKF202401) for financial support
摘 要：Selective modification of peptides has always been a challenging issue. The selective alkylation of peptides can alter the biological activity and physical properties of molecules, and it has gained significant research interest. We herein disclose an intriguing gold-catalyzed alkylation of peptides using bench-stable unactivated alkyl bromides under photoredox catalysis. A wide range of structurally diverse primary, secondary and tertiary alkyl bromides serve as effective coupling partners to precisely connect with the α-C(sp3)–H in glycine residue of peptides. This protocol demonstrates an exceptionally broad scope for alkyl halides and excellent tolerance for a wide range of useful functional groups. A series of relay transformations to construct cyclic peptides, to proceed click reaction and to realize peptide fluorescence labeling further enhance its synthetic practicality. In addition, mechanistic studies and density functional theory(DFT) calculations reveal an inner-sphere and subsequent outersphere single electron transfer(SET) mechanism.
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