Development of optically active polyguanidines that function as asymmetric catalysts

2023 Fiscal Year Final Research Report

• Project/Area Number: 21K05169
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 35010:Polymer chemistry-related
• Research Institution: The University of Tokushima
• Principal Investigator: ARAKAWA Yukihiro 徳島大学, 大学院社会産業理工学研究部(理工学域), 准教授 (70709203)
• Project Period (FY): 2021-04-01 – 2024-03-31
• Keywords: 高分子触媒 / 不斉触媒 / グアニジン / 重付加反応 / 不斉反応

Outline of Final Research Achievements

We synthesized various optically active polyguanidines by the polyaddition reaction of chiral diamines and biscarbodiimides and demonstrated their potential as practical polymeric asymmetric catalysts.
(1) We verified the behavior of equimolar and non-equimolar reactions between chiral secondary diamines and biscarbodiimides to demonstrate the mechanism of the polyaddition reaction. (2) We established a method for preparing biscarbodiimides with alkynyl spacers and demonstrated their polyaddition reaction with chiral primary diamines. (3) We demonstrated the Bronsted base catalysis of optically active polyguanidines and developed the method to design chiral polymeric catalysts by utilizing their noncovalent modification with achiral phosphoric acid diesters.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

キラルなジアミンとビスカルボジイミドの重付加反応に関する研究は前例が無いため、本研究の成果は不斉触媒に限らず様々な機能性高分子材料の設計指針となる重合反応の開発として学術的に極めて重要である。また、当重付加反応による光学活性ポリグアニジンの合成ならびにアキラルリン酸ジエステルによるその非共有結合修飾は、容易に再利用可能な不斉ブレンステッド塩基触媒を極めて迅速かつ簡便に創製可能な実用性の高い手法であり、その端緒を拓いた本研究成果の社会的意義は大きい。