Extremely Difficult Substrate Conversion Based on Catalytic Dehydrogenation and Hydrogen Transfer Reactions Using Renewable Organic Resources

• Project Area: Precise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
• Project/Area Number: 18H04255
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Research Institution: Kyoto University
• Principal Investigator: 藤田 健一 京都大学, 人間・環境学研究科, 教授 (80293843)
• Project Period (FY): 2018-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000); Fiscal Year 2019: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2018: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: 高活性錯体触媒 / 脱水素化反応 / 水素移動反応 / 再生可能資源 / イリジウム / イリジウム触媒 / メチル化反応 / メタノール / エタノール / 酢酸 / 水素

Outline of Annual Research Achievements

本研究の目的は、再生可能な植物資源等から持続的に得られる有機小分子（主としてC1～C3資源）を原料として、高難度分子変換を触媒的に達成することにより、合成化学的価値の高い有機物質の新しい合成手法を開発することである。この目的を実現するために、研究代表者がこれまで取り組んできた「機能性配位子を有するイリジウム錯体触媒による脱水素化ならびに水素移動反応に関する研究」を基盤とし、新規錯体触媒の開発に取り組むとともに、金属錯体反応場の制御を応用したメタノール（C1）、エタノール（C2）、グリセロール（C3）等の小分子を原料に用いた有機合成触媒系の開発を目指してきた。
昨年度までに、１）メタノールをメチル基源とする触媒的メチル化法の開発、ならびに２）エタノール水溶液の脱水素的変換による酢酸合成法の開発等に成功し、C1資源とC2資源の有効活用に関して成果をあげてきた。
本年度は、「グリセロールとジアミンとの反応による含窒素複素環合成」に取り組んだ。グリセロールは、天然油脂から得られ、近年は廃油からのバイオディーゼル油生産にともなって副生するものの、その有効利用はあまり進んでいない。非枯渇性資源から容易に得られるC3原料として、有機合成化学の面からこれを有効活用できればその意義は大きい。この目的にしたがって研究を進め、次の成果を得た。イリジウム錯体触媒を用い、グリセリンとジアミンとの反応による含窒素複素環合成について調査した。例えば、触媒量の含窒素複素環カルベンイリジウム錯体と塩基の存在下、グリセリンとオルト-フェニレンジアミンとの反応を130℃で20時間行ったところ、2-メチルキノキサリンを高収率で得ることができた。本触媒系は、安価で入手が容易なグリセリンを原料として用い、合成化学的価値の高いキノキサリン誘導体を合成するための手法として有用である。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Iridium Complex Immobilized on Custom-Designed Periodic Mesoporous Organosilica as Reusable Catalyst for the Dehydrogenative Oxidation of Alcohols (2020)
  • Author(s): Shimizu, M.; Michikawa, K.; Maegawa, Y.; Inagaki, S.; Fujita, K.
  • Journal Title: ACS Appl. Nano Mater. Volume: 3 Issue: 3 Pages: 2527-2535
  • DOI: 10.1021/acsanm.9b02607
  • Peer Reviewed
• [Journal Article] Metal-Catalyzed Hydrogenation and Dehydrogenation Reactions for Efficient Hydrogen Storage (2020)
  • Author(s): Shimbayashi, T.; Fujita, K.
  • Journal Title: Tetrahedron Volume: 76 Issue: 11 Pages: 130946-130946
  • DOI: 10.1016/j.tet.2020.130946
  • Peer Reviewed
• [Journal Article] Development of Efficient Methods for Organic Synthesis, Hydrogen Storage, and Hydrogen Production Based on Catalytic Dehydrogenation of Organic Molecules (2019)
  • Author(s): 藤田健一
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 77 Issue: 2 Pages: 112-119
  • DOI: 10.5059/yukigoseikyokaishi.77.112
  • NAID: 130007592650
  • ISSN: 0037-9980, 1883-6526
  • Year and Date: 2019-02-01
  • Peer Reviewed
• [Journal Article] Iridium-Catalyzed Transfer Hydrogenation of Ketones and Aldehydes Using Glucose as a Sustainable Hydrogen Donor (2019)
  • Author(s): Yoshida, M.; Hirahata, R.; Inoue, T.; Shimbayashi, T.; Fujita, K.
  • Journal Title: Catalysts Volume: 9 Issue: 6 Pages: 503-503
  • DOI: 10.3390/catal9060503
  • NAID: 120006786925
  • Peer Reviewed / Open Access
• [Journal Article] Effect of a Substituent in Cyclopentadienyl Ligand on Iridium-Catalyzed Acceptorless Dehydrogenation of Alcohols and 2-Methyl-1,2,3,4-tetrahydroquinoline (2019)
  • Author(s): Jeong, J.; Shimbayashi, T.; Fujita, K.
  • Journal Title: Catalysts Volume: 9 Issue: 10 Pages: 846-846
  • DOI: 10.3390/catal9100846
  • Peer Reviewed / Open Access
• [Journal Article] Iridium-Catalyzed Dehydrogenative Lactonization of 1,4-Butanediol and Reversal Hydrogenation: New Hydrogen Storage System Using Cheap Organic Resources (2019)
  • Author(s): Onoda, M.; Nagano, Y.; Fujita, K.
  • Journal Title: Int. J. Hydrogen Energy Volume: 44 Issue: 53 Pages: 28514-28520
  • DOI: 10.1016/j.ijhydene.2019.03.219
  • Peer Reviewed
• [Journal Article] Enviromentally Friendly Synthesis of N-Methylated Nitrogen Heterocycles from an Aqueous Solution of Methylamine and Diols (2019)
  • Author(s): Enomoto, A.; Shimbayashi, T.; Fujita, K.
  • Journal Title: Heterocycles Volume: 98 Issue: 8 Pages: 1119-1129
  • DOI: 10.3987/com-19-14114
  • Peer Reviewed
• [Journal Article] Successive Activation of C-H and C-O Bonds of Vinyl Ethers by a Diphosphine and Hydrido-Bridged Diiridium Complex (2019)
  • Author(s): Takahashi, Y.; Shimbayashi, T.; Fujita, K.
  • Journal Title: Inorganics Volume: 7 Issue: 10 Pages: 121-121
  • DOI: 10.3390/inorganics7100121
  • Peer Reviewed / Open Access
• [Journal Article] Convenient Method for the Production of Deuterium Gas Catalyzed by an Iridium Complex and Its Application to the Deuteration of Organic Compounds (2019)
  • Author(s): Enomoto, A.; Kajita, S.; Fujita, K.
  • Journal Title: Chem. Lett. Volume: 48 Issue: 2 Pages: 106-109
  • DOI: 10.1246/cl.180870
  • NAID: 130007590311
  • Peer Reviewed
• [Journal Article] エタノール水溶液から酢酸を合成する触媒系の開発 (2019)
  • Author(s): 藤田健一
  • Journal Title: クリーンエネルギー Volume: 28(2) Pages: 15-19
  • NAID: 40021799532
• [Journal Article] Development and Application of New Iridium Catalysts for Efficient Dehydrogenative Reactions of Organic Molecules (2019)
  • Author(s): Fujita, K.
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 92 Issue: 2 Pages: 344-351
  • DOI: 10.1246/bcsj.20180301
  • NAID: 130007596693
  • Peer Reviewed / Open Access
• [Journal Article] Dehydrogenative Transformation of Alcoholic Substrates in Aqueous Media Catalyzed by an Iridium Complex Having a Functional Ligand with α-Hydroxypyridine and 4,5-Dihydro-1H-imidazol-2-yl Moieties (2018)
  • Author(s): Yoshida, M.; Wang, H.; Shimbayashi, T.; Fujita, K.
  • Journal Title: Catalysts Volume: 8 Issue: 8 Pages: 312-312
  • DOI: 10.3390/catal8080312
  • NAID: 120006552909
  • Peer Reviewed / Open Access
• [Journal Article] A Sustainable Method for the Synthesis of Acetic Acid Based on Dehydrogenation of an Ethanol-Water Solution Catalyzed by an Iridium Complex Bearing a Functional Bipyridonate Ligand (2018)
  • Author(s): Kuwahara, M.; Nishioka, M.; Yoshida, M.; Fujita, K.
  • Journal Title: ChemCatChem Volume: 10 Issue: 17 Pages: 3636-3640
  • DOI: 10.1002/cctc.201800680
  • Peer Reviewed
• [Journal Article] Efficient and Versatile Catalytic Systems for the N-Methylation of Primary Amines with Methanol Catalyzed by N-Heterocyclic Carbene Complexes of Iridium (2018)
  • Author(s): Toyooka, G.; Tsuji, A.; Fujita, K.
  • Journal Title: Synthesis Volume: 50 Issue: 23 Pages: 4617-4626
  • DOI: 10.1055/s-0037-1610252
  • Peer Reviewed
• [Presentation] イリジウム錯体の触媒的脱水素化能を活用する水素製造ならびに貯蔵法の開発 (2020)
  • Author(s): 藤田健一
  • Organizer: 大阪市立大学大学院理学研究科物質分子系専攻談話会
  • Invited
• [Presentation] Delopment of Efficient Systems for Hydrogen Production Based on Catalytic Activity of Iridium Complexes in Dehydrogenative Reactions (2020)
  • Author(s): Fujita, K.
  • Organizer: 1st International Symposium “Hydrogenomics” combined with 14th International Symposium Hydrogen & Energy
  • Int'l Joint Research
• [Presentation] Transfer Hydrogenation of Carbonyl Compounds Catalyzed by Cp*Iridium Complex Bearing a Functional Ligand Using Glucose as a Sustainable Hydrogen Donor (2020)
  • Author(s): Yoshida, M.; Hirahata, R.; Inoue, T.; Shimbayashi, T.; Fujita, K.
  • Organizer: 日本化学会第100春季年会
• [Presentation] Synthesis of Dicarboxylic Acids by Iridium-Catalyzed Dehydrogenation of Aqueous Solution of Diols (2020)
  • Author(s): Fujita, K.; Toyooka, G.
  • Organizer: 日本化学会第100春季年会
• [Presentation] Iridium Complex-Catalyzed Rapid Dehydrogenation of 2,5-Dimethylpiperazine (2020)
  • Author(s): Jeong, J.; Fujita, K.
  • Organizer: 日本化学会第100春季年会
• [Presentation] 触媒的脱水素化に基づく効率的有機合成ならびに水素製造と貯蔵 (2019)
  • Author(s): 藤田健一
  • Organizer: ファインケミカルズ合成触媒研究会セミナー
  • Invited
• [Presentation] Development of Efficient Systems for Hydrogen Production Based on Catalytic Activity of Iridium Complexes in Dehydrogenative Reactions (2019)
  • Author(s): Fujita, K.
  • Organizer: International Congress on Pure & Applied Chemistry Yangon
  • Int'l Joint Research / Invited
• [Presentation] Synthesis of Acetic Acid Based on Dehydrogenation of an Ethanol-Water Solution Catalyzed by an Iridium Complex Bearing a Functional Ligand (2019)
  • Author(s): Fujita, K.
  • Organizer: The 2nd Japan Germany Singapore Trilateral Symposium on Precision Synthesis and Catalysis
  • Int'l Joint Research / Invited
• [Presentation] アルコール類を原料とする高効率水素製造触媒系の開発 (2019)
  • Author(s): 藤田健一
  • Organizer: あいち産業科学技術総合センター産業技術センターセミナー
  • Invited
• [Presentation] Sustainable Hydrogen Production Based on Dehydrogenation of Alcoholic Substrates in Water Catalyzed by Iridium Complexes Bearing a Functional Ligand (2019)
  • Author(s): Fujita, K.
  • Organizer: The 47th Naito Conference on C-H Bond Activation and Transformation
  • Int'l Joint Research
• [Presentation] Synthesis of 2-Methylquinoxaline Derivatives from Glycerol and Diamines Catalyzed by Iridium Complex (2019)
  • Author(s): Enomoto, A.; Tanaka, T.; Inoue, T.; Shimbayashi, T.; Fujita, K.
  • Organizer: 27th International Society of Heterocyclic Chemistry Congress
  • Int'l Joint Research
• [Presentation] Hydrogen Production Based on Catalytic Activity of Iridium Complexes in Dehydrogenative Reactions (2019)
  • Author(s): Fujita, K.
  • Organizer: The 2nd JGP Chem & ChemEn International Workshop: Sustainability-Oriented Organic Synthesis
  • Int'l Joint Research
• [Presentation] Synthesis of 2-Methylquinoxaline Derivatives from Glycerol and Diamines Catalyzed by Iridium Complex (2019)
  • Author(s): Enomoto, A.; Tanaka, T.; Fujita, K.
  • Organizer: 4th International Symposium on Precisely Designed Catalysts with Customized Scaffolding
  • Int'l Joint Research
• [Presentation] Iridium-Catalyzed Rapid Conversion of 2,5-Dimethylpiperazine into 2,5-Dimethylpyrazine Accompanying the Evolution of Hydrogen (2019)
  • Author(s): Jeong, J.; Fujita, K.
  • Organizer: 4th International Symposium on Precisely Designed Catalysts with Customized Scaffolding
  • Int'l Joint Research
• [Presentation] 機能性PMOとイリジウム錯体の協働効果に基づく触媒的脱水素化反応 (2019)
  • Author(s): 清水嶺之, 道川功実子, 前川佳史, 稲垣伸二, 藤田健一
  • Organizer: 第8回JACI/GSCシンポジウム
• [Presentation] 電子的及び立体的特性の異なるシクロペンタジエニル配位子を持つイリジウム錯体を用いた脱水素化反応 (2019)
  • Author(s): 丁在瑛, 新林卓也, 藤田健一
  • Organizer: 第8回JACI/GSCシンポジウム
• [Presentation] 機能性PMOに固定化されたイリジウム錯体によるアルコールの触媒的脱水素化 (2019)
  • Author(s): 清水嶺之, 道川功実子, 前川佳史, 稲垣伸二, 藤田健一
  • Organizer: 第66回有機金属化学討論会
• [Presentation] 電子的及び立体的特性が異なるCp配位子を有するイリジウム触媒の合成と脱水素化反応における活性調査 (2019)
  • Author(s): 丁在瑛, 新林卓也, 藤田健一
  • Organizer: 錯体化学会第69回討論会
• [Presentation] Synthesis of Dicarboxylic Acids from Diols Accompanying the Evolution of Hydrogen Catalyzed by an Iridium Complex Bearing a Functional Bipyridonate Ligand (2019)
  • Author(s): Toyooka, G.; Fujita, K.
  • Organizer: The 69th Conference of Japan Society of Coordination Chemistry
• [Presentation] イリジウム錯体触媒を用いる2,5-ジメチルピペラジンの高速脱水素化反応 (2019)
  • Author(s): 丁在瑛, 新林卓也, 藤田健一
  • Organizer: 第9回CSJ化学フェスタ2019
• [Presentation] イリジウム錯体の触媒的脱水素化機能に基づく効率的水素製造法の開発 (2019)
  • Author(s): 藤田健一
  • Organizer: 第13回物性科学領域横断研究会
• [Presentation] イリジウム錯体の触媒的脱水素化機能を活用する水素製造・貯蔵法の開発 (2019)
  • Author(s): 藤田健一
  • Organizer: 日本化学会第99春季年会
  • Invited
• [Presentation] イリジウム錯体触媒を用いたエタノール水溶液の脱水素的変換による酢酸合成 (2019)
  • Author(s): 藤田健一
  • Organizer: 「精密制御反応場」第6回公開シンポジウム
• [Presentation] イリジウム触媒による1,4-ブタンジオールの脱水素的ラクトン化とその逆反応 (2019)
  • Author(s): 藤田健一, 小野田光貴, 永野祐大
  • Organizer: 日本化学会第99春季年会
• [Presentation] 有機分子の触媒的脱水素化を基軸とする効率的有機合成ならびに水素貯蔵・水素製造 (2018)
  • Author(s): 藤田健一
  • Organizer: 第113回有機合成シンポジウム
  • Invited
• [Presentation] A Sustainable Method for the Synthesis of Acetic Acid Based on Dehydrogenation of an Ethanol-Water Solution Catalyzed by an Iridium Complex (2018)
  • Author(s): Fujita, K.
  • Organizer: International Symposium in Catalysis and Fine Chemicals 2018 (C&FC 2018)
  • Int'l Joint Research / Invited
• [Presentation] Synthesis of Acetic Acid Based on Dehydrogenation of an Ethanol-Water Solution Catalyzed by an Iridium Complex Bearing a Functional Bipyridonate Ligand (2018)
  • Author(s): Fujita, K.; Kuwahara, M.; Nishioka, M.; Yoshida, M.
  • Organizer: 4th International Conference on Organometallic and Catalysis 2018 (OM&Cat 2018)
  • Int'l Joint Research
• [Presentation] A Sustainable Method for the Synthesis of Acetic Acid from Ethanol-Water Solution by Iridium-Catalyzed Dehydrogenation (2018)
  • Author(s): Fujita, K.; Kuwahara, M.; Nishioka, M.; Yoshida, M.
  • Organizer: JGP Chem & ChemEn International Workshop: Sustainability-Oriented Organic Synthesis
  • Int'l Joint Research
• [Presentation] Iridium Complex-Catalyzed Synthesis of Acetic Acid Based on Dehydrogenation of an Ethanol-Water Solution (2018)
  • Author(s): Fujita, K.; Kuwahara, M.; Nishioka, M.; Yoshida, M.
  • Organizer: 14th International KyotoConference on New Aspects of Organic Chemistry (IKCOC-14)
  • Int'l Joint Research
• [Presentation] Efficient and Versatile N-Methylation of Amines with Methanol Catalyzed by Iridium Complexes Bearing an N-Heterocyclic Carbene Ligand (2018)
  • Author(s): Toyooka, G.; Tsuji, A.; Fujita, K.
  • Organizer: International Symposium in Catalysis and Fine Chemicals 2018 (C&FC 2018)
  • Int'l Joint Research
• [Presentation] Synthesis of Primary Amines by N-Alkylation of Aqueous Ammonia with Alcohols Catalyzed by Water-Soluble Iridium Complexes (2018)
  • Author(s): Shimizu, M.; Furukawa, S.; Morishima, N.; Yamaguchi, R.; Fujita, K.
  • Organizer: International Symposium in Catalysis and Fine Chemicals 2018 (C&FC 2018)
  • Int'l Joint Research
• [Book] Environmentally Benign N-Alkylation of Amines, Ammonia, and Related Compounds Catalyzed by Ir Complexes Using Alcohols as Alkylating Reagents (2019)
  • Author(s): Shimbayashi, T.; Fujita, K.
  • Total Pages: 45
  • Publisher: NOVA Science Publishers
  • ISBN: 9781536147247