Development of New Radical Reactions by Computational Chemistry and Their Realization by Synthetic Experiment

2022 Fiscal Year Final Research Report

• Project/Area Number: 21K18945
• Research Category: Grant-in-Aid for Challenging Research (Exploratory)
• Allocation Type: Multi-year Fund
• Review Section: Medium-sized Section 33:Organic chemistry and related fields
• Research Institution: Hokkaido University
• Principal Investigator: Mita Tsuyoshi 北海道大学, 化学反応創成研究拠点, 特任准教授 (00548183)
• Project Period (FY): 2021-07-09 – 2023-03-31
• Keywords: AFIR法 / 量子化学計算 / ラジカル / アミノ酸 / 逆合成 / 反応経路ネットワーク / 光電子移動触媒 / 光反応

Outline of Final Research Achievements

Using the core technology of the WPI-ICReDD, the AFIR method, new organic radical reactions have been successfully developed. Radical species are known for their high reactivity, which often makes predicting their behavior difficult. However, the AFIR method allows for quick and accurate prediction of radical behavior. This study focused on predicting and realizing functionalization reactions for small molecules such as ethylene and CO2. Specifically, the study successfully developed functionalization reactions of ethylene to imidoyl radicals and sulfonyl radicals, as well as the synthesis of (un)symmetric DPPE derivatives from ethylene. Additionally, the study successfully developed the reaction of CO2 radical anions with stable heteroaromatic rings. These developments are expected to contribute to the advancement of organic synthetic chemistry.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

本研究成果は、反応経路自動探索法（AFIR法）用いて、新しい有機ラジカル反応の開発に成功したことにより、有機合成化学の発展に大きく貢献する。ラジカル種は反応性が非常に高く、予測が難しいことから、これまで理論ベースでの新反応の開発が困難であったが、本研究により、計算化学でラジカル種の挙動を予測しながら新反応を開発する手法が確立された。具体的には、エチレンやCO2などの小分子に対する官能基化反応の開発に成功し、新しい反応開発の手法として注目を集めた。本研究成果は、有機化学分野の発展に貢献すると同時に、新しい医農薬品や機能性材料の化学合成にも役立つものである。