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Development of efficient oxidation catalysts with cheap oxidants

Research Project

Project/Area Number 26630414
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Catalyst/Resource chemical process
Research InstitutionDoshisha University

Principal Investigator

Kodera Masahito  同志社大学, 理工学部, 教授 (00183806)

Project Period (FY) 2014-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2016: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2015: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2014: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Keywords可溶性メタンモノオキシゲナーゼ / 酸素分子活性化 / 安価な酸化剤 / カルボキシル基含有二核化配位子 / アルカン水酸化 / カルボキシラト基の効果 / A/K比 / 触媒回転数 / 酸化システムの開発 / カルボキシラトリッチな配位環境 / カルボキシラト基を持つ二核化配位子 / アルカン類の酸化反応 / カルボン酸含有二核鉄錯体 / 側鎖アルキル基の疎水性 / 高い触媒能力 / 過酸化水素 / 二核鉄錯体 / シクロヘキサン / アダマンタン / 3級/2級の選択性 / 酸化活性種 / syn-to-anti構造変化 / 反応速度の大きな加速 / 大きな同位体効果 / 高性能酸化触媒 / アルカン活性化 / high-spin diiron(IV)
Outline of Final Research Achievements

Soluble methane monooxygenases (sMMO) are nonheme diiron enzymes that catalyze oxidation of various organic compounds. Diiron centers of sMMO are coordinated by two imidazole donors of His residues and by four carboxylate donors of Glu residues. In this study we synthesized four different carboxylate-rich dinucleating ligands, 1,2-bis(N-benzyl-2-amino- methyl-6-pyridyl)ethane-N,N’-diglycine (H2Lgly), 1,2-bis(6-aminomethyl-2-pyridyl)ethane-N,N’-di- (norleucine) (H2Lnle), 1,2-bis(6-aminomethyl-2-pyridyl)ethane-N,N’-di(N-methylnorleucine) (H2LMenle), 1,2-bis(N-(9-anthracene)-2-aminomethyl-6-pyridyl)ethane (H2Lanthracenegly). These ligands form diiron complexes, which rapidly and efficiently catalyzed the oxidation of alkanes with m-CPBA as an oxidant to show high A/K ratio, large turnover number, large turnover frequency in the catalytic oxidations. These are attained by the carboxylate-rich coordination environment.

Report

(4 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Research-status Report
  • 2014 Research-status Report
  • Research Products

    (36 results)

All 2017 2016 2015 2014 Other

All Journal Article (3 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 3 results,  Acknowledgement Compliant: 3 results) Presentation (27 results) (of which Int'l Joint Research: 8 results,  Invited: 7 results) Book (2 results) Remarks (2 results) Patent(Industrial Property Rights) (2 results)

  • [Journal Article] Specific Enhancement of Catalytic Activity by a Dicopper Core in Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide Catalyzed by Copper Complexes2017

    • Author(s)
      Tomokazu Tsuji, Antonius Andre Zaoputra, Yutaka Hitomi, Kaoru Mieda, Takashi Ogura, Yoshihito Shiota, Kazunari Yoshizawa, Hiroyasu Sato, Masahito Kodera*
    • Journal Title

      Angewandte Chemie International Edition

      Volume: in press

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Formation and High Reactivity of the anti-Dioxo Form of High- Spin m-Oxodioxodiiron(IV) as the Active Species That Cleaves Strong C2016

    • Author(s)
      Masahito Kodera,* Shin Ishiga, Tomokazu Tsuji, Katsutoshi Sakurai, Yutaka Hitomi, Yoshihito Shiota, P. K. Sajith, Kazunari Yoshizawa, Kaoru Mieda, and Takashi Ogura
    • Journal Title

      Chemistry A European Journal

      Volume: 17 Issue: 17 Pages: 1-14

    • DOI

      10.1002/chem.201600048

    • Related Report
      2016 Annual Research Report 2015 Research-status Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Roles of Carboxylate Donors in O-O Bond Scission of Peroxodiiron(III) to High-Spin Oxodiiron(IV) with a New Carboxylate-Containing Dinucleating Ligand2014

    • Author(s)
      M. Kodera, T. Tsuji, T. Yasunaga, Y. Kawahara, T. Hirano, Y. Hitomi, T. Nomura, T. Ogura, Y. Kobayashi, Sajith P. K., Y. Shiota, and K. Yoshizawa
    • Journal Title

      Chem. Sci.

      Volume: 5 Issue: 6 Pages: 2282-2292

    • DOI

      10.1039/c3sc51541a

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] DNAの酸化的切断を促進する二核銅錯体の開発2017

    • Author(s)
      角谷 優樹・鳥取 智樹・福井 克樹・人見 穣・小寺 政人
    • Organizer
      第97回日本化学会春季年会
    • Place of Presentation
      慶応大学日吉キャンパス(神奈川県・横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] G-quadruplex DNA と選択的に結合する二核銅錯体の開発2017

    • Author(s)
      齋藤 樹・角谷 優樹・福井 克樹・人見 穣・小寺 政人
    • Organizer
      第97回日本化学会春季年会
    • Place of Presentation
      慶応大学日吉キャンパス(神奈川県・横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] 二核金属錯体が触媒するDNAの酸化的切断に及ぼす大環状アミン配位部位の効果2017

    • Author(s)
      鳥取 智樹・福井 克樹・角谷 優樹・人見 穣・小寺 政人
    • Organizer
      第97回日本化学会春季年会
    • Place of Presentation
      慶応大学日吉キャンパス(神奈川県・横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] キノリン側鎖を持つ新規二核化配位子の二核銅錯体の合成,構造, 基質酸化反応2017

    • Author(s)
      八塚駿・辻朋和・人見穣・小寺政人
    • Organizer
      第97回日本化学会春季年会
    • Place of Presentation
      慶応大学日吉キャンパス(神奈川県・横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] Reactivity and identification of intermediates formed upon reaction of dinickel(II) complex with H2O22017

    • Author(s)
      ZAOPUTRA, Antonius Andre; TSUJI, Tomokazu; HITOMI, Yutaka; MIEDA, Kaoru; OGURA, Takashi; KODERA, Masahito
    • Organizer
      第97回日本化学会春季年会
    • Place of Presentation
      慶応大学日吉キャンパス(神奈川県・横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] Bioinspired dimetal complexes: extremely high catalytic activity for the oxidation of benzene with hydrogen peroxide2016

    • Author(s)
      Masahito Kodera
    • Organizer
      8th Asian Biological Inorganic Chemistry
    • Place of Presentation
      Auckland (New Zealand)
    • Year and Date
      2016-12-04
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 固体高分子形燃料電池の空気極触媒の開発: 高い酸化還元電位を示す新規二核銅錯体2016

    • Author(s)
      鉢形真也・辻朋和・人見穣・小寺政人
    • Organizer
      第49回酸化反応討論会
    • Place of Presentation
      徳島大学(徳島県・徳島市)
    • Year and Date
      2016-11-12
    • Related Report
      2016 Annual Research Report
  • [Presentation] カルボン酸含有二核鉄錯体が触媒する高速・高選択的アルカン酸化:酸化触媒活性に及ぼす側鎖アルキル基の効果2016

    • Author(s)
      笹邉 真史・辻 朋和・人見 穣・小寺 政人
    • Organizer
      第49回酸化反応討論会
    • Place of Presentation
      徳島大学(徳島県・徳島市)
    • Year and Date
      2016-11-12
    • Related Report
      2016 Annual Research Report
  • [Presentation] 二核銅錯体が触媒するH2O2を用いた高速高選択的酸化反応2016

    • Author(s)
      辻 朋和・人見 穣・小寺 政人
    • Organizer
      第49回酸化反応討論会
    • Place of Presentation
      徳島大学(徳島県・徳島市)
    • Year and Date
      2016-11-12
    • Related Report
      2016 Annual Research Report
  • [Presentation] キノリン側鎖を持つ新規二核化配位子の二核銅錯体の合成,構造, 基質酸化反応2016

    • Author(s)
      八塚駿・辻朋和・人見穣・小寺政人
    • Organizer
      第49回酸化反応討論会
    • Place of Presentation
      徳島大学(徳島県・徳島市)
    • Year and Date
      2016-11-12
    • Related Report
      2016 Annual Research Report
  • [Presentation] Reaction Intermediates upon Direct Oxidation of Benzene to Phenol with H2O2 Catalyzed by Dinickel Complexes Stabilized by Dinucleating Ligands2016

    • Author(s)
      Antonius Andre Zaoputra, 辻 朋和, 人見 穣, 小寺政人
    • Organizer
      第49回酸化反応討論会
    • Place of Presentation
      徳島大学(徳島県・徳島市)
    • Year and Date
      2016-11-12
    • Related Report
      2016 Annual Research Report
  • [Presentation] 固体高分子形燃料電池の空気極触媒の開発:高い酸化還元電位を示す新規二核銅錯体の合成2016

    • Author(s)
      鉢形真也・辻 朋和・北山 航・人見 穣・小寺政人
    • Organizer
      第66回錯体化学会討論会
    • Place of Presentation
      福岡大学(福岡県・福岡市)
    • Year and Date
      2016-09-10
    • Related Report
      2016 Annual Research Report
  • [Presentation] DNA切断を促進する二核金属錯体の細胞導入2016

    • Author(s)
      角谷優樹・福井克樹・人見 穰・小寺政人
    • Organizer
      第66回錯体化学会討論会
    • Place of Presentation
      福岡大学(福岡県・福岡市)
    • Year and Date
      2016-09-10
    • Related Report
      2016 Annual Research Report
  • [Presentation] 高スピン二核鉄(IV)酸化活性種:生成過程の分光学的追跡、高いC-H結合開裂能力、大きなKIE、高選択的酸化反応2016

    • Author(s)
      岸本竜弥・櫻井克俊・辻 朋和・石賀 慎・人見 穣・小寺政人
    • Organizer
      第66回錯体化学会討論会
    • Place of Presentation
      福岡大学(福岡県・福岡市)
    • Year and Date
      2016-09-10
    • Related Report
      2016 Annual Research Report
  • [Presentation] Extremely High Turnover for Direct Oxidation of Benzene to Phenol with H2O2 Catalyzed by Dicopper Complexes2016

    • Author(s)
      Tomokazu TSUJI, Yutaka HITOMI, Hiroyasu SATO, Masahito KODERA
    • Organizer
      第66回錯体化学会討論会
    • Place of Presentation
      福岡大学(福岡県・福岡市)
    • Year and Date
      2016-09-10
    • Related Report
      2016 Annual Research Report
  • [Presentation] Direct Oxidation of Benzene to Phenol with H2O2 Catalyzed by New Dinickel Complexes Stabilized by Dinucleating Ligands2016

    • Author(s)
      Antonius Andre ZAOPUTRA, Tomokazu TSUJI, Yutaka HITOMI, Masahito KODERA
    • Organizer
      第66回錯体化学会討論会
    • Place of Presentation
      福岡大学(福岡県・福岡市)
    • Year and Date
      2016-09-10
    • Related Report
      2016 Annual Research Report
  • [Presentation] Formation and high reactivity of anti-dioxo form of high-spin m-oxodioxodiiron(IV) that cleaves a strong C-H bond2016

    • Author(s)
      Masahito Kodera
    • Organizer
      42nd International Conference on Coordination Chemistry
    • Place of Presentation
      Brest (France)
    • Year and Date
      2016-07-02
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] DNA cleavage activity and Cell Insertion of Binuclear Metal Complexes as Anti-Cancer Drugs2016

    • Author(s)
      Yuki Kadoya, Kenta Aso, Katsuki Fukui, Yutaka Hitomi, Masahito Kodera
    • Organizer
      42nd International Conference on Coordination Chemistry
    • Place of Presentation
      Brest (France)
    • Year and Date
      2016-07-02
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Development of Dicopper Complexes as a Cathode Catalyst for Polymer Electrolyte Fuel Cell: Control of the Redox Potential2016

    • Author(s)
      Shinya Hachigata Kou Kitayama, Tomokazu Tsuji, Yutaka Hitomi, Masahito Kodera
    • Organizer
      42nd International Conference on Coordination Chemistry
    • Place of Presentation
      Brest (France)
    • Year and Date
      2016-07-02
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Electronic effect of ligand on high-spin m-oxodioxodiiron(IV)2016

    • Author(s)
      Katsutoshi Sakurai, Masahito Kodera
    • Organizer
      42nd International Conference on Coordination Chemistry
    • Place of Presentation
      Brest (France)
    • Year and Date
      2016-07-02
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Direct Oxidation of Benzene to Phenol with H2O2 Catalyzed by Dinickel Complexes Stabilized by Dinucleating Ligands2016

    • Author(s)
      Antonius Andre Zaoputra, Tomokazu Tsuji, Yutaka Hitomi, Masahito Kodera
    • Organizer
      42nd International Conference on Coordination Chemistry
    • Place of Presentation
      Brest (France)
    • Year and Date
      2016-07-02
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Formation and High Reactivity of High-Spin Anti-Dioxo Diiron(IV) as the Real Active Species to Cleave a Strong C-H Bond2015

    • Author(s)
      Masahito Kodera
    • Organizer
      Golden Jubilee Chemistry Conference-2nd Japan-Singapore-Taiwan Trilateral Symposium in Coordination Chemistry-
    • Place of Presentation
      Singapore
    • Year and Date
      2015-08-05
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Highly reactive anti-dioxo high-spin diiron(IV)2015

    • Author(s)
      Msahito Kodera
    • Organizer
      19th International Conference of Cytochrome P450
    • Place of Presentation
      Tokyo, Japan
    • Year and Date
      2015-06-12
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] sMMOの高い酸化力を再現する二核鉄錯体触媒の開発2015

    • Author(s)
      小寺政人
    • Organizer
      分子研研究会
    • Place of Presentation
      愛知県岡崎市 分子科学研究所
    • Year and Date
      2015-01-06 – 2015-01-07
    • Related Report
      2014 Research-status Report
    • Invited
  • [Presentation] High-Spin Oxodiiron(IV) Active Species [O=Fe(IV)]2O that Cleaves Strong C-H Bond: Formation Mechanism and Efficient Alkane Oxidation with H2O22014

    • Author(s)
      Masahito Kodera
    • Organizer
      7th Asian Biological Inorganic Chemistry Conference
    • Place of Presentation
      Gold Coast
    • Year and Date
      2014-11-30 – 2014-12-05
    • Related Report
      2014 Research-status Report
    • Invited
  • [Presentation] 6-hpa配位子のanti-dioxo high-spin diiron(IV)酸化活性種の生成と反応性:過酸化水素を酸化剤とする高効率高選択的アルカン水酸化2014

    • Author(s)
      石賀慎・河原由佳・辻朋和・人見穣・小寺政人
    • Organizer
      錯体化学会
    • Place of Presentation
      中央大学
    • Year and Date
      2014-09-18 – 2014-09-20
    • Related Report
      2014 Research-status Report
  • [Presentation] Formation and Reactivity of Anti-Dioxo High-Spin Diiron(IV) Active Species [O=Fe(IV)]2O2014

    • Author(s)
      Masahito Kodera
    • Organizer
      日英錯体化学シンポジウム
    • Place of Presentation
      中央大学
    • Year and Date
      2014-09-17 – 2014-09-18
    • Related Report
      2014 Research-status Report
    • Invited
  • [Book] フロンティア生物無機化学2016

    • Author(s)
      伊東忍、青野重利、林高史、増田秀樹、廣田俊、藤井浩、小寺政人、城宜嗣、樋口芳樹、高妻孝光、杉本秀樹、小倉尚志、民秋均、大久保敬、正岡重行、小江誠司、久枝良雄、青木伸、菊池和也、上野隆史、小谷明
    • Total Pages
      527
    • Publisher
      三共出版
    • Related Report
      2016 Annual Research Report
  • [Book] クライトン生物無機化学2016

    • Author(s)
      塩谷光彦(監訳)小寺政人(共訳)
    • Total Pages
      354
    • Publisher
      東京化学同人
    • Related Report
      2015 Research-status Report
  • [Remarks] 分子生命化学研究室Doshisha University

    • Related Report
      2016 Annual Research Report
  • [Remarks] 分子生命化学研究室

    • URL

      http://www1.doshisha.ac.jp/~mkodera1/index.html

    • Related Report
      2015 Research-status Report
  • [Patent(Industrial Property Rights)] 二核化配位子又は二核金属錯体2017

    • Inventor(s)
      小寺 政人、福井 克樹、角谷 優樹
    • Industrial Property Rights Holder
      小寺 政人、福井 克樹、角谷 優樹
    • Industrial Property Rights Type
      特許
    • Filing Date
      2017-02-22
    • Related Report
      2016 Annual Research Report
  • [Patent(Industrial Property Rights)] フェノール系化合物の製造方法2016

    • Inventor(s)
      小寺 政人、辻 朋和
    • Industrial Property Rights Holder
      小寺 政人、辻 朋和
    • Industrial Property Rights Type
      特許
    • Filing Date
      2016-04-26
    • Related Report
      2016 Annual Research Report

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Published: 2014-04-04   Modified: 2018-03-22  

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