Synthesis of Branch-Type Cyclophane Tetramers Having a Multivalently Enhanced Guest-Binding Ability

• 作者: Chihiro Nada Osamu Hayashida Shuhei Kusano
• 来源期刊: 化学工程与科学期刊(英文)
• 学科: 化学
• 关键词: CYCLOPHANE HOST-GUEST CHEMISTRY MULTIVALENT Effect
• 年，卷（期）: 2019,（1）
• 页码范围: 76-86
• 页数: 11页
• 分类号: O6

摘要

A cationic branch-type cyclophane tetramer (1a) was synthesized by introducing three Boc-protected cyclophane derivatives into a N-acetylated tetraaza[6.1.6.1]paracy-clophane derivative as a core skeleton through DCC condensation, followed by removal of the external Boc-protecting groups. Cationic cyclophane tetramer 1a exhibited a high affinity toward an anionic and hydrophobic fluorescent guest, TNS, with binding constant of 4.8 × 105 M-1. This value of 1a was about 80-fold larger than that of the corresponding monomeric cyclophane for the identical guest, reflecting multivalent effect on the guest binding. As for electrostatic recognition, the obtained binding constant of 1a was one order of magnitude larger than that of an analogous anionic cyclophane tetramer (1b) for the identical guest. These enhanced guest-binding abilities of 1a were easily evaluated by fluorescence titration experiments.