Development of flexibly designable organic reducing agents and their application(Fostering Joint International Research)

2019 Fiscal Year Final Research Report

• Project/Area Number: 15KK0186
• Research Category: Fund for the Promotion of Joint International Research (Fostering Joint International Research)
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: Osaka University
• Principal Investigator: Tsurugi Hayato 大阪大学, 基礎工学研究科, 准教授 (60432514)
• Project Period (FY): 2016 – 2019
• Keywords: 有機ケイ素還元剤 / 低原子価錯体 / 還元的切断 / メタセシス反応 / 前周期遷移金属 / 環化付加反応

Outline of Final Research Achievements

"Single-site heterogeneous catalyst" is a new type catalyst having advantages of both homogeneous and heterogeneous catalysts. Catalyst activation of such the heterogeneous catalyst is generally required high reaction temperature. By using an organosilicon reducing agent applicable to reduction of various metal complexes, activation of such the heterogeneous catalysts is accomplished under the mild reaction conditions, resulted in lowering the thermal energy required for the use of heterogeneous catalysts. Low catalyst activation temperature enabled us to apply the heterogeneous catalyst system for low-temperature metathesis reactions using functionalized alkenes. In addition, low-valent species generated by the organosilicon reducing agent was effective for the cleavage of a N=N bond of azobenzene and catalytic pyrrole formation with internal alkynes via metal-catalyzed cycloaddition reaction.

Free Research Field

有機金属化学

Academic Significance and Societal Importance of the Research Achievements

不均一系触媒の活性化、特に単一の活性中心が表面に存在する「シングルサイト性不均一系触媒」に対して、金属錯体の還元反応に利用可能な有機ケイ素還元剤を用いることにより、温和な条件で触媒活性化が可能であるとする、不均一系触媒の利用時のエネルギーコストの大幅な削減につながる研究成果を得た。有機反応剤により不均一系触媒の表面状態を劇的に変えることが可能である本還元剤の役割は、不均一系触媒の改質や失活後の再活性化につながる基盤的知見となる点で、学術的にも意義深い成果である。