School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology, Brisbane, Queensland 4001, Australia.
Org Biomol Chem. 2018 Nov 14;16(44):8569-8578. doi: 10.1039/c8ob02304b.
This paper describes the use of the copper(i)-catalysed azide-alkyne cycloaddition reaction in an active metal template methodology for the synthesis of [2]rotaxanes both in solution and on polymer resins. The use of TentaGel resin beads has allowed the rotaxane functionalised solid supports to be characterized by 1H HR MAS NMR. Whereas previous research in the assembly of interlocked architectures on surfaces are complicated by the concurrent attachment of large proportions of non-interlocked byproducts, in this example over 80% of the functionalization is the desired interlocked rotaxane. The inclusion of zinc metalloporphyrins in the structure of the [2]rotaxane thread allowed the position of the macrocycle to be 'switched' upon the addition of competing base, removal of the metal or appropriate choice of solvent. Investigations into the pseudocooperative effect the mechanical bond has on the metalloporphyrin-macrocycle coordination equilibrium were performed and the associated effective molarity in this [2]rotaxane was calculated to be 120 mM.
本文描述了铜（i）催化的叠氮化物-炔烃环加成反应在活性金属模板法中的应用，用于在溶液中和聚合物树脂上合成[2]轮烷。使用 TentaGel 树脂珠允许通过 1H HR MAS NMR 对轮烷功能化的固体载体进行表征。虽然以前在表面上组装互锁结构的研究受到同时附着大量非互锁副产物的影响，但在本例中，超过 80%的功能化是所需的互锁轮烷。在[2]轮烷线的结构中包含锌金属卟啉允许大环的位置在添加竞争碱基、去除金属或选择适当溶剂时“切换”。对机械键对金属卟啉-大环配位平衡的伪协同效应进行了研究，并计算了该[2]轮烷中的相关有效摩尔浓度为 120mM。
