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Carborane Guests for Cucurbit[7]uril Facilitate Strong Binding and On-Demand Removal
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2020-11-30 , DOI: 10.1021/jacs.0c09361
Anna Kataki-Anastasakou 1 , Jonathan C Axtell 1 , Selena Hernandez 1 , Rafal M Dziedzic 1 , Gary J Balaich 2 , Arnold L Rheingold 3 , Alexander M Spokoyny 1 , Ellen M Sletten 1
Affiliation  

High-affinity guests have been reported for the macrocyclic host cucurbit[7]uril (CB[7]), enabling widespread applications, but hindering CB[7] materials from being returned to their guest-free state for reuse. Here, we present polyhedral boron clusters (carboranes) as strongly binding, yet easily removable, guests for CB[7]. Aided by a Pd-catalyzed coupling of an azide anion, we prepared boron-functionalized 9-amino-ortho-carborane that binds to CB[7] with a Ka ≈ 1010 M-1. Upon basic treatment, ortho-carborane readily undergoes deboronation to yield anionic nido-carborane, a poor guest for CB[7], facilitating recovery of guest-free CB[7]. We showcase the utility of the modified ortho-carborane guest by recycling a CB[7]-functionalized resin. With this report, we introduce stimuli-responsive decomplexation as an additional consideration in the design of high-affinity host-guest complexes.

中文翻译:

用于 Cucurbit[7]uril 的碳硼烷客体促进强结合和按需去除

据报道,大环宿主葫芦[7]脲(CB[7])具有高亲和力,可实现广泛应用,但阻碍了CB[7]材料恢复到无客体状态以供重复使用。在这里,我们提出多面体硼簇(碳硼烷)作为 CB [7] 的强结合且易于去除的客体。在 Pd 催化的叠氮阴离子偶联的帮助下,我们制备了硼功能化的 9-氨基邻碳硼烷,它以 Ka ≈ 1010 M-1 与 CB[7] 结合。在碱性处理后,邻碳硼烷很容易发生脱硼反应,生成阴离子基碳硼烷,它是 CB 的不良客体 [7],促进了无客体 CB [7] 的回收。我们通过回收 CB[7]-官能化树脂来展示改性邻碳硼烷客体的效用。有了这份报告,
更新日期:2020-11-30
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