2026-06-02 京都大学
ホウ素モノマーにおける非古典的水素結合を活用した立体規則性ビニルポリマー合成 作成：大内研究室
＜関連情報＞
- https://www.t.kyoto-u.ac.jp/ja/research/topics/20260602-1
- https://www.nature.com/articles/s41467-026-73603-1
ビニルホウ素モノマーの立体規則性制御重合における分子内の非古典的水素結合の役割 The key role of an intramolecular non-classical hydrogen bond of vinylboron monomer for stereoselective polymerization
Hiroshi Suzuki,Tsuyoshi Nishikawa & Makoto Ouchi
Nature Communications Published:01 June 2026
DOI:https://doi.org/10.1038/s41467-026-73603-1
Abstract
Stereoselective polymerization has long been a central research focus in polymer science because tacticity plays a crucial role in regulating the physical properties and functions of vinyl polymers. However, synthetic strategies that enable control over both isotacticity and syndiotacticity remain limited. Herein, we report an impact of an intramolecular non-classical hydrogen bond between the vinyl and pendant groups in the monomer on tacticity-controlled polymerization. A vinylboron monomer, in which the boron atom is protected by an anthranilamide bearing a tetrahydrofuran (THF) ring with a chiral center, undergoes syndio-specific polymerization, and the subsequent oxidation of the polymer side chains afforded syndiotactic poly(vinyl alcohol)s (PVAs, rr: up to 63%). Computational studies suggest the hydrogen bond between vinyl proton and oxygen in the THF ring plays a key role in syndiotactic regulation. The interpretation is further supported by a contrasting result obtained by replacing the oxygen atom in the THF ring with a methylene group, which leads to the formation of isotactic PVA (mm: 71%).
