Development of metal-free catalyst for the reduction of simple ketones using computational chemistry.

2023 Fiscal Year Final Research Report

• Project/Area Number: 21K05064
• 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: Iwate University
• Principal Investigator: Korenaga Toshinobu 岩手大学, 理工学部, 教授 (70335579)
• Co-Investigator(Kenkyū-buntansha): 岡崎 雅明 弘前大学, 理工学研究科, 教授 (20292203)
• Project Period (FY): 2021-04-01 – 2024-03-31
• Keywords: 計算化学主導型触媒開発 / FLP触媒 / 水素化反応 / 遷移状態 / 溶媒効果

Outline of Final Research Achievements

Interplay-type catalyst development combining computational and experimental methods was used to achieve metal-free asymmetric FLP-catalyzed asymmetric hydrogenation of simple ketones. We designed the chiral Lewis bases as the catalysts based on quantum chemical calculations, and actually synthesized 10 different catalysts and observed their selectivities, but only obtained results with much lower selectivities than expected. A close examination of the results, both experimentally and computationally, suggested that the predictions were inaccurate due to a dissociation between the calculated transition states with solvent effects and the actual transition state during the actual reaction. The cause of this dissociation was considered to be the influence of real solvent molecules, which were not taken into account in the calculations. Therefore, we have started to develop a calculation system that evaluates real solvent molecules.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

インタープレイ型触媒開発は新触媒を効率的に開発するための強力な手法となり得るが、まだ黎明期であり、実験化学者が容易に利用できる手法ではない。そこで研究代表者は、将来におけるインタープレイ法利用の一般化を目指し、この手法を用いた計算化学主導型の触媒開発を実施した。対象とする不斉FLP触媒は メタルフリーな水素化触媒として注目されているが、単純ケトンを用いた不斉水素化の難易度は非常に高い。そこで、本研究では単純ケトンの不斉水素化で95% ee越えを達成できる新規不斉FLP触媒を世界に先駆けて開発することを目的とした。以上のように、研究の進め方と研究結果、両方で学術的意味を有する。