Development of highly active organic molecular catalysts for hydrogen extract-release from biologically produced organic materials

2023 Fiscal Year Final Research Report

• Project/Area Number: 20K05473
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
• Research Institution: Tokyo University of Agriculture and Technology
• Principal Investigator: Okamoto Akiko 東京農工大学, 工学(系)研究科(研究院), 講師 (30512777)
• Project Period (FY): 2020-04-01 – 2024-03-31
• Keywords: 有機分子触媒 / 水素引き抜き-放出 / 酸化還元能 / 非共平面的芳香環集積分子 / peri-アロイルナフタレン / 高歪ピナコール

Outline of Final Research Achievements

In order to develop novel organic molecular catalyst that adjusts the redox ability by changing the molecular three-dimensional structure, understanding the spatial structure of naphthalene diketone compounds and diol compounds, and investigation of the reduction-oxidation reaction behavior of the diketone-diol pairs have carried out. First, various diketone compounds were synthesized, and the correlation between molecular modification and changes in the steric environment near the carbonyl groups was derived from the various conformations in the crystal. Furthermore, the diol compounds are stabilized in solution by adopting a conformation that accumulates intramolecular hydrogen bonds. Next, the reaction behavior analysis has revealed the correlation between spatial organization and reactivity, i.e. the closely flexible carbonyl configuration of the diketone compound is linked to the ease of reduction, and the increased strain of the diol is linked to the ease of oxidation.

Free Research Field

構造有機化学

Academic Significance and Societal Importance of the Research Achievements

遷移金属と異なり有機分子は酸化数を多様に変化させられない。その課題を解決すべく既存の酸化還元型有機分子触媒は酵素や色素の酸化還元部位を組み込んでいるが基質の適用範囲は限られる。本研究では酸化還元能を変化させるための新たなパラダイムとして，結合形成・解裂点周辺の芳香環の空間配置が「非共平面的で強固に固定されていない」有機分子の利用を追求した。非共平面的なジケトン化合物の空間構造の精密な把握と反応挙動の整理に基づき，分子立体構造の変化が還元-酸化の受け易さと密接にリンクしていることを明らかにした。本成果は「酸化還元能を調節可能」な全く新しい概念の有機分子触媒のカテゴリーの創造に寄与するものである。