Universität Heidelberg, Anorganisch-Chemisches Institut und Interdisziplinäres Zentrum für Wissenschaftliches Rechnen, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Chemistry. 2022 Apr 22;28(23):e202200249. doi: 10.1002/chem.202200249. Epub 2022 Mar 18.
Copper complexes of patellamides have shown catalytic activity in a variety of reactions but their biological function remains unknown. There are significant differences between the natural macrocycles and synthetic analogues in the various catalytic activities. It therefore is essential to be able to perform in vivo and ex vivo reference measurements with the natural patellamide macrocycles, very similar derivatives and a large range of synthetic analogues. The preparative method described allows for a highly adaptable synthetic process producing building blocks for a large range of patellamide derivatives: apart from natural compounds, a new synthetic patellamide was prepared that does not have any substituents at any of the four heterocycles. Together with the variation of substituents at the aliphatic backbone, this allowed to elucidate the catalytic activity for phosphoester hydrolysis as a function of the structure and dynamics of the dicopper(II)-patellamide complexes, both by experiment and DFT-based mechanistic studies.
贝壳杉烷酰胺的铜配合物在多种反应中表现出催化活性，但它们的生物学功能仍然未知。在各种催化活性方面，天然大环化合物和合成类似物之间存在显著差异。因此，能够对天然贝壳杉烷酰胺大环化合物、非常相似的衍生物和大量合成类似物进行体内和体外参考测量是至关重要的。所描述的制备方法允许进行高度适应性的合成过程，从而产生大量贝壳杉烷酰胺衍生物的构建块：除了天然化合物外，还制备了一种新的合成贝壳杉烷酰胺，其在四个杂环中的任何一个上都没有取代基。与脂肪主链上取代基的变化相结合，这使得通过实验和基于 DFT 的机理研究来阐明磷酸酯水解的催化活性与二铜（II）-贝壳杉烷酰胺配合物的结构和动力学之间的关系。
