Construction of reaction environments relying on fluorophilic effects and development of reactions utilizing these effects

2022 Fiscal Year Final Research Report

• Project/Area Number: 19K07006
• 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: Meijo University
• Principal Investigator: Matsugi Masato 名城大学, 農学部, 教授 (90324805)
• Project Period (FY): 2019-04-01 – 2023-03-31
• Keywords: フルオロフィリック効果 / 反応場 / 配位子 / 配座 / 不斉合成

Outline of Final Research Achievements

The appropriate design of reaction field space is an important tool to control and improve stereoselectivity, regioselectivity, and functional group selectivity in synthetic organic chemistry. In this research project, we have utilized the stacking phenomenon between fluorous tags, which relies on the fluorophilic effect, for the "formation of reaction-field space" to achieve an effective asymmetric catalytic reaction system.
As a result, it was found that the absolute configuration of the adduct is reversed in the asymmetric Henry reaction when a bisoxazoline copper complex is used, which is expected to undergo a conformational change due to the intramolecular fluorophilic effect. In other words, it is clear that asymmetric recognition can be reversed by simply introducing two fluorous tags to an easily available naturally occurring chiral source.

Free Research Field

有機化学

Academic Significance and Societal Importance of the Research Achievements

有機合成分野においてこれまで展開されてきたフルオラスケミストリーは,フルオラス分子と非フルオラス分子間の相間分離による簡易分離技術が基盤となっていた。この領域に初めて分子レベルでの「フルオラス-スタッキング現象による反応場空間構築」の概念を導入し,不斉炭素-炭素結合形成反応の立体選択性制御に応用した。
フルオラスタグを標的触媒リガンドに導入するだけで新たな反応場空間を形成させ,立体選択的反応の選択性改良が可能になり,フルオラスケミストリーのブレークスルーとなり得る新領域を開拓できた。