官能基化ナノケージの高効率な合成法を開発～機能性有機ホスト材料の開発に向けて～

2025-07-25 東京科学大学

図. テンプレート法による内部官能基化オリゴフェニレンケージの合成

＜関連情報＞

• https://www.isct.ac.jp/ja/news/k117rvgi406g
• https://pubs.acs.org/doi/10.1021/jacs.5c04400

共有結合テンプレート誘導合成による内側機能化オリゴフェニレンケージの合成 Covalent Template-Guided Synthesis of endo-Functionalized Oligophenylene Cages

Kosuke Ono,Fumito Sasamori,Hatsune Izawa,Hiroki Baba,Shion Masano,Ryutaro Shirataki,Hidetoshi Kawai,and Kei Goto
Journal of the American Chemical Society  Published: June 25, 2025
DOI:https://doi.org/10.1021/jacs.5c04400

Abstract

Herein, we demonstrate the efficient covalent template-guided synthesis of lantern-shaped endo-functionalized oligophenylene cages 1. The synthetic route proceeds by virtue of cooperative bond formations via Suzuki–Miyaura cross-coupling and the use of covalent templates through intermolecular 6-fold coupling among three molecules. Using templates 4a and 4b, template-containing cages 6a and 6b were constructed in 68 and 36% yield, respectively, and the subsequent quantitative removal of the templates led to the corresponding OH- and NH₂-functionalized cages 1a and 1b. In the absence of templates, intermolecular 4-fold coupling among three molecules afforded cages 1a and 1b in only 7 and 1% yield, respectively. The proposed mechanism for the efficient intermolecular 6-fold coupling was corroborated by electrospray ionization mass spectrometry (ESI-MS) monitoring experiments. Moreover, OH- and NH₂-functionalized cages were found to encapsulate l-TrpOMe (G1) and diphenyl phosphate (G2), respectively, within their cavities through interactions between polar functional groups.