Study on the Mechanism and the General Application of Microwave Specific Effects on Synthetic Organic Chemistry

2023 Fiscal Year Final Research Report

• Project/Area Number: 21K05073
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Keio University
• Principal Investigator: Yamada Tohru 慶應義塾大学, 理工学部(矢上), 教授 (40296752)
• Project Period (FY): 2021-04-01 – 2024-03-31
• Keywords: マイクロ波特異効果 / 触媒的不斉合成反応 / エナンチオ選択性 / 反応加速 / 環化反応 / 熱環化付加反応

Outline of Final Research Achievements

Since the acceleration of organic synthetic reactions by the microwave was reported in 1986, improvements in efficiency have been reported in various reaction systems. Although reaction acceleration is generally interpreted as a direct heating effect on the reaction system, microwave　-specific effects, such as reducing the amount of catalyst and improving chemical selectivity, have been discussed. The author succeeded in experimentally verifying the separation of microwave-specific effects from thermal effects in asymmetric synthetic reactions. In this study, it was confirmed that the chemical yield was improved with maintaining enantioselectivity in the asymmetric Nazarov cyclization-fluorination reaction, and the microwave-specific effect was confirmed. Furthermore, in the asymmetric Diels-Alder reaction, microwave-specific effects were observed based on slight reaction acceleration with maintaining enantioselectivity.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

マイクロ波特異効果は2008年にマイクロ波化学の先駆的な研究者による論文で否定され，その後定説とされてきた。2013年ころ新たな実験事実に基づくマイクロ波特異効果に関する議論が再燃したが，マイクロ波特異効果の存在を明確に示す実験結果は報告されていないのが現状であった。報告者は不斉合成反応においてマイクロ波特異効果を熱的効果から分離する実験的検証に成功し，マイクロ波による反応加速が加熱効果だけではないことを明確に示し，本研究ではマイクロ波特異効果の一般化を目指した。