Dramatic synergistic effect by the combination of a "rigid" chiral bicyclic skeleton with steric bulkiness and a "flexible" achiral linker for the development of highly effective asymmetric synthesis

2022 Fiscal Year Final Research Report

• Project/Area Number: 18K06550
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 47010:Pharmaceutical chemistry and drug development sciences-related
• Research Institution: Tokyo University of Science, Yamaguchi
• Principal Investigator: Matsunaga Hirofumi 山陽小野田市立山口東京理科大学, 薬学部, 教授 (10274713)
• Project Period (FY): 2018-04-01 – 2023-03-31
• Keywords: 有機化学 / 不斉触媒 / 不斉合成 / 不斉有機触媒 / Michael反応 / 配座固定 / リンカー

Outline of Final Research Achievements

We previously demonstrated that the combination of a “rigid” chiral bicyclic cis-1,2-diamine skeleton with the steric bulkiness and a “flexible” achiral linker was newly designed as a bifunctional organocatalyst framework and showed excellent catalytic activity of up to 0.05 mol% in an amine-thiourea organocatalyzed asymmetric Michael reaction. In this study, based on the “rigidity-flexibility synergistic framework” concept, we optimized the structure of the initial bifunctional organocatalyst. We succeeded in creating organocatalysts with higher catalytic activity and enantioselectivity. We also prepared bifunctional organocatalysts derived from the indane skeleton and polymer-anchored organocatalysts based on this design theory, which exhibited high catalytic activity.

Free Research Field

有機化学

Academic Significance and Societal Importance of the Research Achievements

不斉有機触媒は “環境に優しい”触媒として近年富に注目を集めているものの一般に多量の触媒量や長い反応時間を要すことが多く、効率性や実用性が高いとは言えない。本研究では配座固定「堅い」母核と「柔らかい」側鎖との組み合わせによる二官能性有機分子触媒の新たな設計理論により、低触媒量で高効率・高立体選択的な不斉合成を可能にし得る新規有機分子触媒創生の可能性を実証した。本設計理論を利用した別骨格による新たな触媒の開発、並びに、高分子固定化による再利用可能な資源循環型高機能有機分子触媒の開発など、真に汎用性と実用性に優れた省資源・省エネルギー型新規不斉触媒の創成に繋がるものと期待している。