Development of catalytic oxidation of alkanes using water as an oxygen source

• Project/Area Number: 20H02734
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: University of Hyogo (2021-2022); Nagoya University (2020)
• Principal Investigator: Yoshihiro Miyake 兵庫県立大学, 理学研究科, 教授 (00347270)
• Project Period (FY): 2020-04-01 – 2023-03-31
• Project Status: Completed (Fiscal Year 2022)
• Budget Amount: ¥18,460,000 (Direct Cost: ¥14,200,000、Indirect Cost: ¥4,260,000); Fiscal Year 2022: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000); Fiscal Year 2021: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000); Fiscal Year 2020: ¥12,740,000 (Direct Cost: ¥9,800,000、Indirect Cost: ¥2,940,000)
• Keywords: 酸化反応 / ジアザポルフィリン / 二酸化炭素 / 還元反応 / 水 / アルカン

Outline of Research at the Start

本申請課題では、アルカンと水からアルコールと水素を光駆動により合成する反応（光をエネルギー源、水を酸素源として用いたアルカンの触媒的酸化反応）の達成を目指す。その実現のためには、鍵反応として①アルカンの直接的酸化反応と②水と光を用いたオキソ錯体生成反応を開発することが必要であり、その達成には金属オキソ錯体の効率的生成とその反応性の向上が重要となる。本研究では、それを可能にする触媒として電子受容性π共役骨格を配位子にもつ遷移金属錯体を設計・合成し、その反応性を明らかにする。

Outline of Final Research Achievements

In this project, C-H bond oxidation of alkanes catalyzed by diazaporphyrin metal complexes was performed. It was found that the diazaporphyrin metal complexes exhibit higher reactivity than conventional porphyrin metal complexes, and the difference in reactivity was attributed to the electron acceptivity of the main skeleton. The reactivity was further exploited to catalyze the C-H bond fluorination of alkanes.

Academic Significance and Societal Importance of the Research Achievements

得られた成果はポルフィリンの主骨格にsp2-窒素原子を導入することで金属錯体の電子受容性を向上させるという手法が触媒の反応性を向上させる有効な戦略となり得るということを示した点で意義がある。

Research Products

• [Journal Article] One-dimensional stacking array of 10,20-diphenyl-5,15-diazaporphyrin metal complexes (2023)
  • Author(s): Mori Shiho、Sakurai Takahiro、Nishimura Tsubasa、Fukui Norihito、Miyake Yoshihiro、Shinokubo Hiroshi
  • Journal Title: Journal of Porphyrins and Phthalocyanines Volume: 27 Issue: 07n10 Pages: 1035-1041
  • DOI: 10.1142/s1088424622500997
  • Peer Reviewed
• [Journal Article] Easily Switchable 18π‐, 19π‐, and 20π‐Conjugation of Diazaporphyrin Double‐Pincer Bispalladium Complexes (2023)
  • Author(s): Sakurai Takahiro、Hiraoka Yuya、Tanaka Hisaaki、Miyake Yoshihiro、Fukui Norihito、Shinokubo Hiroshi
  • Journal Title: Angewandte Chemie International Edition Volume: 62 Issue: 12
  • DOI: 10.1002/anie.202300437
  • Peer Reviewed
• [Journal Article] Stepwise N‐Methylation of Ruthenium and Cobalt 5,15‐Diazaporphyrins: Post‐Functionalization of Porphyrinoid Catalysts (2022)
  • Author(s): Nishijo Mayu、Mori Shiho、Nishimura Tsubasa、Shinokubo Hiroshi、Miyake Yoshihiro
  • Journal Title: Chemistry An Asian Journal Volume: 17 Issue: 14
  • DOI: 10.1002/asia.202200305
  • Peer Reviewed
• [Journal Article] Cationic Nickel(II) Pyridinophane Complexes: Synthesis, Structures and Catalytic Activities for C–H Oxidation (2021)
  • Author(s): Tsubasa Nishimura ,Yuki Ando ,Hiroshi Shinokubo , and Yoshihiro Miyake
  • Journal Title: Chemistry Letters Volume: 50 Issue: 5 Pages: 1049-1052
  • DOI: 10.1246/cl.210074
  • NAID: 130008040440
  • Peer Reviewed
• [Journal Article] ron hexamesityl-5,15-diazaporphyrin: synthesis, structure and catalytic use for direct oxidation of sp3 C–H bonds (2021)
  • Author(s): Tsubasa Nishimura ,Takahiro Sakurai ,Hiroshi Shinokubo , and Yoshihiro Miyake
  • Journal Title: Dalton Transactions Volume: 50 Issue: 18 Pages: 6343-6348
  • DOI: 10.1039/d1dt00893e
  • Peer Reviewed
• [Journal Article] Manganese(III) 5,15-diazaporphyrins: Synthesis, properties, and catalytic use for benzylic C?H fluorination (2021)
  • Author(s): Mori Shiho、Nishimura Tsubasa、Shinokubo Hiroshi、Miyake Yoshihiro
  • Journal Title: Journal of Porphyrins and Phthalocyanines Volume: 25 Issue: 10n12 Pages: 991-996
  • DOI: 10.1142/s1088424621500887
  • Peer Reviewed
• [Journal Article] Peripherally Arylated 2,8-Diazaperylenes from Anthracene Diimide: Synthesis and Oxidative Annulation (2021)
  • Author(s): Sakurai Takahiro、Nakazato Takumi、Shinokubo Hiroshi、Miyake Yoshihiro
  • Journal Title: Organic Letters Volume: 23 Issue: 6 Pages: 2099-2103
  • DOI: 10.1021/acs.orglett.1c00253
  • Peer Reviewed
• [Journal Article] Cationic nickel(II) pyridinophane complexes: Synthesis, structures and catalytic activities for C-H oxidation (2021)
  • Author(s): Nishimura Tsubasa、Ando Yuki、Shinokubo Hiroshi、Miyake Yoshihiro
  • Journal Title: Chemistry Letters Volume: 50
  • NAID: 130008040440
  • Peer Reviewed
• [Journal Article] Iron(III) 5,15-Diazaporphyrin Catalysts for the Direct Oxidation of C(sp3)?H Bonds (2020)
  • Author(s): Nishimura Tsubasa、Ikeue Takahisa、Shoji Osami、Shinokubo Hiroshi、Miyake Yoshihiro
  • Journal Title: Inorganic Chemistry Volume: 59 Issue: 21 Pages: 15751-15756
  • DOI: 10.1021/acs.inorgchem.0c02166
  • Peer Reviewed
• [Journal Article] Synthesis and crystal packing structures of 2,7-diazapyrenes with various alkyl groups at 1,3,6,8-positions (2020)
  • Author(s): Takumi Nakazato, Wakana Matsuda, Tsuneaki Sakurai, Shu Seki, Hiroshi Shinokubo, Yoshihiro Miyake
  • Journal Title: Chemistry Letters Volume: 49 Issue: 5 Pages: 465-468
  • DOI: 10.1246/cl.200083
  • NAID: 130007840170
  • Peer Reviewed
• [Presentation] N,N’-ジメチル-2,7-ジアザピレニウムジカチオンの還元と還元体の性質、 (2021)
  • Author(s): 仲里 巧・竹腰 遥・忍久保 洋・三宅 由寛
  • Organizer: 日本化学会第101春季年会
• [Presentation] 2,7-ジアザピレン骨格を基盤とする水素結合性有機構造体の構築 (2021)
  • Author(s): 小田原 正浩・七野 正典・松田 亮太郎・忍久保 洋・三宅 由寛
  • Organizer: 日本化学会第101春季年会