2021 Fiscal Year Final Research Report

Exploration of catalysis of N(5) unmodified flavin molecules

Research Project

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Project/Area Number	19K05457
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	The University of Tokushima
Principal Investigator	IMADA Yasushi 徳島大学, 大学院社会産業理工学研究部(理工学域), 教授 (60183191)
Co-Investigator(Kenkyū-buntansha)	南川慶二徳島大学, 教養教育院, 教授 (70250959) 荒川幸弘徳島大学, 大学院社会産業理工学研究部(理工学域), 准教授 (70709203)
Project Period (FY)	2019-04-01 – 2022-03-31
Keywords	有機分子触媒 / フラビン触媒 / フォトレドックス触媒 / 酸素添加反応 / 脱水素反応 / フロー反応
Outline of Final Research Achievements	Based on simulations of enzymatic functions governed by flavoenzymes, we pioneered the catalytic function of N(5)-unsubstituted flavin molecules and demonstrated their potential as practical organocatalysts. (1) The cooperative effect of carboxyl groups introduced into the N(5)-unsubstituted flavin molecules was demonstrated, and design guidelines for N(5)-unsubstituted flavin molecules with monooxygenase-type catalysis were provided. (2) The oxidase-type catalysis of flavin-containing porous polymers and flavin-containing spherical polymers was verified, and their application to a flow reaction system using them as fixed-bed catalysts was demonstrated. (3) Photolyase-type catalysis was demonstrated by developing oxyamination of aldehydes through the cooperative catalysis of a flavin molecule catalyst and a secondary amine catalyst, and was applied to a flow reaction system.
Free Research Field	有機合成化学
Academic Significance and Societal Importance of the Research Achievements	(1)のフラビン分子とカルボキシル基の協働効果によるモノオキシゲナーゼ触媒機能の発現の実証とこれに基づく触媒の設計指針及び(3)のフラビン分子のフォトレドックス触媒機能の実証と分子設計に基づく高機能触媒の開発はいずれも前例のないものであり、フラビン分子の新規触媒機能の開発として学術的に極めて重要である。(2)のフラビン分子のオキシダーゼ触媒作用によるヒドラジンの脱水素反応を鍵とするオレフィンの水素化反応と(3)のフラビン分子のフォトレドックス触媒採用によるアルデヒドのオキシアミノ化反応のフロー反応システムへの展開は、フラビン分子触媒による分子変換反応の実用性を示すものであり社会的意義は大きい。