Department of Chemistry & Biochemistry, The University of Alabama, Box 870336, Tuscaloosa, AL 35487-0336, USA.
Chem Rec. 2022 Dec;22(12):e202200190. doi: 10.1002/tcr.202200190. Epub 2022 Sep 8.
Nucleosides represent one of the key building blocks of biochemistry. There is significant interest in the synthesis of nucleoside-derived materials for applications as probes, biochemical models, and pharmaceuticals. Palladium-catalyzed cross-coupling reactions are effective methods for making covalent modification of carbon and nitrogen sites on nucleobases under mild conditions. Water-soluble catalysts derived from palladium and hydrophilic ligands, such as tris(3-sulfonatophenyl)phosphine trisodium (TPPTS), are efficient catalysts for a range of coupling reactions of unprotected halonucleosides. Over the past two decades, these methods have been extended to direct functionalization of halonucleotides, as well as RNA and DNA oligonucleotides (ONs) containing halogenated bases. These methods can be run under biocompatible conditions, including examples of Suzuki coupling of modified DNA in whole cells and tissue samples. In this account, development of this methodology by our group and others is highlighted along with the extension of these catalyst systems to modification of nucleotides and ONs.
核苷是生物化学的关键组成部分之一。人们对合成核苷衍生材料非常感兴趣，这些材料可用作探针、生化模型和药物。钯催化的交叉偶联反应是在温和条件下对碱基上的碳和氮位点进行共价修饰的有效方法。钯和亲水性配体（如三（3-磺酸钠基）苯基）膦三钠盐（TPPTS）衍生的水溶性催化剂是一系列未保护卤代核苷的高效偶联反应催化剂。在过去的二十年中，这些方法已扩展到直接对卤代核苷酸以及含卤碱基的 RNA 和 DNA 寡核苷酸（ON）进行功能化。这些方法可以在生物相容的条件下进行，包括在整个细胞和组织样本中进行修饰 DNA 的 Suzuki 偶联的例子。在本报告中，突出了我们小组和其他小组在该方法学方面的发展，以及这些催化剂系统在核苷酸和 ON 修饰方面的扩展。
