Della Sala Flavio, Doerner Benedicte, Webb Simon J
Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Manchester Institute of Biotechnology, University of Manchester, 131 Princess Street, Manchester M1 7DN, UK.
Org Biomol Chem. 2025 Sep 10. doi: 10.1039/d5ob01226k.
Zinc(II) bis(triazolyl)(pyridyl)amine (Zn(BTPA)) complexes on the end of α-amino-iso-butyric acid (Aib) foldamers are able to transfer chirality from bound anions to the helical foldamer body. Zn(BTPA) could be obtained by simple synthetic methodology that allowed a range of functional groups to be installed around the binding site, exemplified with a fluorophore, a macrocyclic bridge and Aib itself. Changing functional group did not prevent chiral ligands from controlling foldamer conformation, although differences in complexation kinetics and equilibria were observed. Addition of acetate gave a 2 : 1 foldamer : acetate intermediate at sub-stoichiometric acetate; a similar intermediate was implied during titration with Boc-Pro. A bulkier phosphate ligand or a more sterically hindered site did not form similar intermediates. The modular construction of Zn(BTPA)-capped foldamers will allow these conformational relays to be installed in a wide range of biomimetic constructs.
α-氨基异丁酸（Aib）折叠体末端的锌（II）双（三唑基）（吡啶基）胺（Zn（BTPA））配合物能够将手性从结合的阴离子转移到螺旋折叠体主体上。Zn（BTPA）可通过简单的合成方法获得，该方法允许在结合位点周围安装一系列官能团，以荧光团、大环桥和Aib本身为例。尽管观察到络合动力学和平衡存在差异，但改变官能团并不妨碍手性配体控制折叠体构象。加入乙酸盐在亚化学计量的乙酸盐条件下生成了2:1的折叠体:乙酸盐中间体；在用Boc-Pro滴定过程中也暗示了类似的中间体。体积更大的磷酸盐配体或空间位阻更大的位点不会形成类似的中间体。Zn（BTPA）封端的折叠体的模块化构建将使这些构象传递能够安装在各种仿生构建体中。
