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Creation of Transition-metal-Oxido Complexes for Direct C-H Bond Hydroxylation

Planned Research

Project AreaMolecule Activation Directed toward Straightforward Synthesis
Project/Area Number 22105007
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionOsaka University

Principal Investigator

Itoh Shinobu  大阪大学, 工学(系)研究科(研究院), 教授 (30184659)

Co-Investigator(Renkei-kenkyūsha) SUGIMOTO Hideki  大阪大学, 大学院工学研究科, 准教授 (00315970)
FUJIEDA Nobutaka  大阪大学, 大学院工学研究科, 助教 (00452318)
MORIMOTO Yuma  大阪大学, 大学院工学研究科, 特任助教 (20719025)
Project Period (FY) 2010-04-01 – 2016-03-31
Project Status Completed (Fiscal Year 2015)
Budget Amount *help
¥110,370,000 (Direct Cost: ¥84,900,000、Indirect Cost: ¥25,470,000)
Fiscal Year 2014: ¥15,080,000 (Direct Cost: ¥11,600,000、Indirect Cost: ¥3,480,000)
Fiscal Year 2013: ¥15,990,000 (Direct Cost: ¥12,300,000、Indirect Cost: ¥3,690,000)
Fiscal Year 2012: ¥16,770,000 (Direct Cost: ¥12,900,000、Indirect Cost: ¥3,870,000)
Fiscal Year 2011: ¥16,640,000 (Direct Cost: ¥12,800,000、Indirect Cost: ¥3,840,000)
Fiscal Year 2010: ¥45,890,000 (Direct Cost: ¥35,300,000、Indirect Cost: ¥10,590,000)
Keywordsオキソ錯体 / 水酸化反応 / 触媒 / 銅 / ニッケル / オスミウム / ジオール化 / 金属酵素モデル / 銅活性酸素錯体 / 酸素化反応 / ジオール化反応 / スーペルオキソ錯体 / 有機ラジカル錯体 / 人工金属酵素 / 炭素―水素結合活性化 / 金属オキソ錯体 / 活性酸素錯体 / 反応機構 / 金属オキソ種 / C-H結合活性化 / 金属酵素 / C-H結合の活性化 / オスミウム錯体 / 銅錯体
Outline of Final Research Achievements

Selective hydroxylation of hydrocarbons is one of the most important but is still very difficult chemical transformation reactions in synthetic organic chemistry and industrial chemistry. In this study, we have developed transition-metal active-oxygen speceis supported by simple pyridyl(alkylamine) ligands, which are capable of performing selective hydroxylation reactions of aliphatic and aromatic compounds using molecular oxygen or hydrogen peroxide as an oxidant. We have also succeeded to developed osmium complexes supported by the same series of pyridyl(alkylamine) ligands, which can catalyze efficient cis-dihydroxylation and 1,2-aminohydroxylation reactions of olefins. Mechanistic studies on the above reactions have been performed in detail to get insights into the structure and properties of the transition-metal active-oxygen intermediates.

Report

(6 results)
  • 2015 Final Research Report ( PDF )
  • 2014 Annual Research Report
  • 2013 Annual Research Report
  • 2012 Annual Research Report
  • 2011 Annual Research Report
  • 2010 Annual Research Report
  • Research Products

    (50 results)

All 2016 2015 2014 2013 2012 2011 Other

All Journal Article (23 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 23 results,  Acknowledgement Compliant: 7 results,  Open Access: 5 results) Presentation (21 results) (of which Int'l Joint Research: 6 results,  Invited: 20 results) Book (3 results) Remarks (3 results)

  • [Journal Article] A Model for the Active-Site Formation Process in DMSO Reductase Family Molybdenum Enzymes Involving Oxido-Alcoholato and Oxido-Thiolato Molybdenum(VI) Core Structures2016

    • Author(s)
      Hideki Sugimoto, Masanori Sato, Kaori Asano, Takeyuki Suzuki, Kaoru Mieda, Takashi Ogura, Takashi Matsumoto, Logan J. Giles, Amrit Pokhrel, Martin L. Kirk, and Shinobu Itoh
    • Journal Title

      Inorg. Chem.

      Volume: 55 Issue: 4 Pages: 1542-1550

    • DOI

      10.1021/acs.inorgchem.5b02395

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Cerium-Complex-Catalyzed Oxidation of Arylmethanols under Atmospheric Pressure of Dioxygen and Its Mechanism through a Side-On m-Peroxo Dicerium(IV) Complex2016

    • Author(s)
      Mitali Paul, Satoru Shirase, Yuma Morimoto, Laurent Mathey, Balasubramanian Murugesapandian, Shinji Tanaka, Shinobu Itoh, Hayato Tsurugi, and Kazushi Mashima
    • Journal Title

      Chem. Eur. J.

      Volume: 22 Issue: 12 Pages: 4008-4014

    • DOI

      10.1002/chem.201503846

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Oxidative Cyclization of 1,5-Dienes with Hydrogen Peroxide Catalyzed by an Osmium(III) Complex: Synthesis of cis- Tetrahydrofurans2016

    • Author(s)
      Hideki Sugimoto, Takayuki Kanetake, Kazuki Maeda, and Shinobu Itoh
    • Journal Title

      Org. Lett.

      Volume: 18 Issue: 6 Pages: 1246-1249

    • DOI

      10.1021/acs.orglett.6b00064

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Direct Hydroxylation of Benzene to Phenol Using Hydrogen Peroxide Catalyzed by Nickel Complexes Supported by Pyridylalkylamine Ligands2015

    • Author(s)
      Yuma Morimoto, Shuji Bunno, Nobutaka Fujieda, Hideki Sugimoto, and Shinobu Itoh
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 137 Issue: 18 Pages: 5867-5870

    • DOI

      10.1021/jacs.5b01814

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] cis-1,2-Aminohydroxylation of Alkenes Involving a Catalytic Cycle of Osmium(III) and Osmium(V) Centers: Os(V)(O)(NHTs) Active Oxidant with a Macrocyclic Tetradentate Ligand2015

    • Author(s)
      Hideki Sugimoto, Akine Mikami, Kenichiro Kai, P. K. Sajith, Yoshihito Shiota, Kazunari Yoshizawa, Kaori Asano, Takeyuki Suzuki, and Shinobu Itoh
    • Journal Title

      Inorg. Chem.

      Volume: 54 Issue: 14 Pages: 7073-7082

    • DOI

      10.1021/acs.inorgchem.5b01083

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Generation, Characterization, and Reactivity of a CuII-Alkylperoxide/Anilino Radical Complex: Insight into the O-O Bond Cleavage Mechanism2015

    • Author(s)
      Sayantan Paria, Takehiro Ohta, Yuma Morimoto, Takashi Ogura, Hideki Sugimoto, Nobutaka Fujieda, Kei Goto, Kaori Asano, Takeyuki Suzuki, and Shinobu Itoh
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 137 Issue: 34 Pages: 10870-10873

    • DOI

      10.1021/jacs.5b04104

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Developing Mononuclear Copper Active-Oxygen Complexes Relevant to Reactive Intermediates of Biological Oxidation Reactions2015

    • Author(s)
      Shinobu Itoh
    • Journal Title

      Acc. Chem. Res.

      Volume: 48 Issue: 7 Pages: 2066-2074

    • DOI

      10.1021/acs.accounts.5b00140

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper complexes supported by an N2S-tridentate ligand as active site models of copper monooxygenases2014

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      Dalton Trans.

      Volume: 42 Issue: 12 Pages: 4871-4877

    • DOI

      10.1039/c3dt52952e

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Oxo-sulfido- and oxo-selenido-molybdenum(VI) complexes possessing dithiolene ligand related to the active sites of hydroxylases of molybdoenzymes: Low temperature preparation and characterisation2013

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      Chem. Commun.

      Volume: 49 Issue: 39 Pages: 4358-4360

    • DOI

      10.1039/c2cc35345h

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] A new series of bis(ene-1,2-dithiolato)tungsten(IV), -(V), -(VI) complexes as reaction centre models of tungsten enzymes: preparation, crystal structures and spectroscopic properties2013

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      Dalton Trans.

      Volume: 42 Issue: 9 Pages: 3059-3070

    • DOI

      10.1039/c2dt32179c

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Copper Complexes of the Non-innocent β-Diketiminate Ligand Containing Phenol Groups2013

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      Dalton Trans.

      Volume: 42 Issue: 7 Pages: 2438-2444

    • DOI

      10.1039/c2dt32413j

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] C–H Bond Activation of the Supporting Ligand in an Osmium(III) Complex with H2O2: Formation of an Organometallic Osmium(IV) Complex2013

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      Inorg. Chem.

      Volume: 52 Issue: 2 Pages: 543-545

    • DOI

      10.1021/ic302169k

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Crystal Structures Of Copper-Depleted And Copper-Bound Fungal Pro-Tyrosinase: Insights Into Endogenous Cysteine-Dependent Copper Incorporation2013

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      J. Biol.Chem.

      Volume: 288 Issue: 30 Pages: 22128-22140

    • DOI

      10.1074/jbc.m113.477612

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Redox Properties of Mononuclear Copper(II)-Superoxide Complex2013

    • Author(s)
      Shinobu Itoh
    • Journal Title

      Inorg. Chem.

      Volume: 52 Issue: 18 Pages: 10431-10437

    • DOI

      10.1021/ic401261z

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Oxo-carboxylato-molybdenum(VI) complexes possessing dithiolene ligand related to the active site of type II class of DMSOR family of molybdoenzymes2013

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      Dalton Trans.

      Volume: 42 Issue: 45 Pages: 15927-15930

    • DOI

      10.1039/c3dt51485d

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Artificial Dicopper Oxidase: Rational Reprogramming of Bacterial Metallo-β-lactamase into a Catechol Oxidase;2012

    • Author(s)
      Nobutaka Fujieda
    • Journal Title

      Chem. Asian J.

      Volume: 7 Issue: 6 Pages: 1203-1207

    • DOI

      10.1002/asia.201101014

    • Related Report
      2012 Annual Research Report 2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper(I)-Dioxygen Reactivity in a Sterically Demanding Tripodal Tetradentate tren Ligand. Formation and Reactivity of a Mononuclear Copper(II) End-on Superoxo Complex2012

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      Eur. J. Inorg. Chem.

      Volume: 2012 Issue: 29 Pages: 4574-4578

    • DOI

      10.1002/ejic.201200177

    • Related Report
      2012 Annual Research Report 2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Heterolytic Alkylhydroperoxide O-O Bond Cleavage by Copper(I) Complexes2012

    • Author(s)
      Tetsuro Tano
    • Journal Title

      Eur. J. Inorg. Chem.

      Volume: 2012 Issue: 26 Pages: 4099-4103

    • DOI

      10.1002/ejic.201200555

    • Related Report
      2012 Annual Research Report 2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Active Site Models for the CuB Site of Peptidylclycine α-Hydroxylating Monooxygenase and Dopamine β-Monooxygenase2012

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      Inorg. Chem.

      Volume: 51 Issue: 17 Pages: 9465-9480

    • DOI

      10.1021/ic301272h

    • Related Report
      2012 Annual Research Report 2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] (165) An Osmium(III)/Osmium(V) Redox Couple Generating OsV(O)(OH) Center for cis-1,2-Dihydroxylation of Alkenes with H2O2: Os Complex with a Nitrogen- based Tetradentate Ligand2012

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      J Am. Chem. Soc.

      Volume: 134 Issue: 46 Pages: 19270-19280

    • DOI

      10.1021/ja309566c

    • Related Report
      2012 Annual Research Report 2011 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Multifunctions of MelB, a Fungal Tyrosinase from Aspergillus oryzae2012

    • Author(s)
      S.Itoh, et al
    • Journal Title

      ChemBioChem.

      Volume: 13 Pages: 193-201

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Reactions of Copper(II)-Phenol Systems with O_2. Models for TPQ Biosynthesis in Copper Amine Oxidases2011

    • Author(s)
      S.Itoh, et al
    • Journal Title

      Inorg.Chem.

      Volume: 50 Pages: 1633-1647

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Reactivity of copper(II)-alkylperoxo complexes2011

    • Author(s)
      S.Itoh, et al
    • Journal Title

      Dalton Trans.

      Volume: 40 Pages: 10326-10336

    • Related Report
      2010 Annual Research Report
    • Peer Reviewed
  • [Presentation] Models for Active Oxygen Intermediates of Mononuclear Copper Monooxygenases2016

    • Author(s)
      Shinobu Itoh
    • Organizer
      18th National Symposium in Chemistry of Chemical Research Society of India
    • Place of Presentation
      Panjab University, Chandigarh, India
    • Year and Date
      2016-02-05
    • Related Report
      2014 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Selective Hydroxylation of Benzene to Phenol with Hydrogen Peroxide Catalyzed by Ni-Complexes2015

    • Author(s)
      Shinobu Itoh
    • Organizer
      IUPAC-2015 (World Chemistry Congress)
    • Place of Presentation
      Busan, Korea
    • Year and Date
      2015-08-09
    • Related Report
      2014 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Mononuclear Copper Active-oxygen Complexes with A Non-innocent Supporting Ligand2015

    • Author(s)
      Shinobu Itoh
    • Organizer
      17th International Conference on Biological Inorganic Chemistry (ICBIC17)
    • Place of Presentation
      Beijing, Chaina
    • Year and Date
      2015-07-20
    • Related Report
      2014 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Controlling Copper(I)-Dioxygen Reactivity by Pyridylalkylamine Tridentate Ligands2015

    • Author(s)
      Shinobu Itoh, Tsukasa Abe, and Yuma Morimoto
    • Organizer
      5th Asian Conference on Coordination Chemistry (ACCC5)
    • Place of Presentation
      The University of Hong Kong, Hong Kong
    • Year and Date
      2015-07-12
    • Related Report
      2014 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Models for Active Oxygen Intermediates of Copper Monooxygenases2015

    • Author(s)
      Shinobu Itoh
    • Organizer
      19th International Conference on Cytochrome P450 (ICCP450)
    • Place of Presentation
      Tokyo, Japan
    • Year and Date
      2015-06-12
    • Related Report
      2014 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Developing Mononuclear Copper Reaction Site for Oxygen Activation2015

    • Author(s)
      Shinobu Itoh
    • Organizer
      Gordon Research Conference
    • Place of Presentation
      Ventura, California, USA
    • Year and Date
      2015-01-25
    • Related Report
      2014 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Copper Complexes of Non-innocent β-Diketiminate Ligands2013

    • Author(s)
      Shinobu Itoh
    • Organizer
      16th International Conference of Biological Inorganic Chemiastry (ICBIC16)
    • Place of Presentation
      Grenoble, France
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Copper Complexes of Non-innocent β-Diketiminate Ligands2013

    • Author(s)
      Shinobu Itoh
    • Organizer
      15th Asian Chemical Congress (15ACC)
    • Place of Presentation
      Singapore
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Ligand Design for Oxygen Activation by Copper Complexes2013

    • Author(s)
      Shinobu Itoh
    • Organizer
      The 2nd Canada-Japan Joint Symposium on Coordination Chemistry
    • Place of Presentation
      Okinawa
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Oxygen Activation Chemistry at Mononuclear Copper Reaction Center2013

    • Author(s)
      Shinobu Itoh
    • Organizer
      The 4th Asian Conference on Coordination Chemistry (ACCC4)
    • Place of Presentation
      Jeju, South Korea
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Recent Advances in Copper-Dioxygen Chemistry2013

    • Author(s)
      Shinobu Itoh
    • Organizer
      Symposium on Modern Trends in Inorganic Chemistry–XV
    • Place of Presentation
      Roorkee, India
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] 金属オキソ錯体の新展開2012

    • Author(s)
      伊東 忍
    • Organizer
      第40回オルガノメタリックセミナー
    • Place of Presentation
      京都大学化学研究所
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Reactivity of Copper(II)-Superoxo Complexes2012

    • Author(s)
      Shinobu Itoh
    • Organizer
      9th Japan-Chaina Joint Symposium on Metal Cluster Compounds
    • Place of Presentation
      Fukuoka, Japan
    • Related Report
      2012 Annual Research Report 2011 Annual Research Report
    • Invited
  • [Presentation] Reactivity of Mononuclear Copper(II) Active-Oxygen Species2012

    • Author(s)
      Shinobu Itoh
    • Organizer
      Symposium of the Activation of Dioxygen and Homogeneous Catalytic Oxidation (ADHOC 2012)
    • Place of Presentation
      Jerusalem, Israel
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Reactivity of Mononuclear Copper(II) End-on Superoxo Complexes2012

    • Author(s)
      Shinobu Itoh
    • Organizer
      40th International Conference of Coordination Chemistry (ICCC40)
    • Place of Presentation
      Valensia, Spein
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Modeling Mononuclear Copper Reaction Centers of Copper Monooxygenases2012

    • Author(s)
      Shinobu Itoh
    • Organizer
      The 6th Biological Inorganic Chemistry Conference (AsBIC-6)
    • Place of Presentation
      Hong Kong, China
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Reactivity of Mononuclear Copper(II) Active-Oxygen Species2012

    • Author(s)
      Shinobu Itoh
    • Organizer
      Symposium of the Activation of Dioxygen and Homogeneous Catalytic Oxidation
    • Place of Presentation
      Jerusalem, Israel
    • Related Report
      2011 Annual Research Report
    • Invited
  • [Presentation] Reactivity of Mononuclear Copper(II) End-on Superoxo Complexes2012

    • Author(s)
      Shinobu Itoh
    • Organizer
      40th International Conference of Coordination Chemistry
    • Place of Presentation
      Valencia, Spain
    • Related Report
      2011 Annual Research Report
    • Invited
  • [Presentation] Modeling Mononuclear Copper Reaction Centers of Copper Monooxygenases2012

    • Author(s)
      Shinobu Itoh
    • Organizer
      The 6th Biological Inorganic Chemistry Conference
    • Place of Presentation
      Hong Kong, Chaina
    • Related Report
      2011 Annual Research Report
    • Invited
  • [Presentation] 金属オキソ錯体の新展開2012

    • Author(s)
      伊東 忍
    • Organizer
      第40回オルガノメタリックセミナー
    • Place of Presentation
      宇治市
    • Related Report
      2011 Annual Research Report
    • Invited
  • [Presentation] Aliphatic Hydroxylation Catalyzed by Nickel(II) Complexes2011

    • Author(s)
      S.Itoh
    • Organizer
      14^<th> Asian Chemical Congress
    • Place of Presentation
      Bangkok, Thailand(招待講演)
    • Year and Date
      2011-09-06
    • Related Report
      2010 Annual Research Report
  • [Book] Chemical Science of π-Electron Systems2015

    • Author(s)
      Shinobu Itoh and Yuma Morimoto
    • Total Pages
      1000
    • Publisher
      Springer
    • Related Report
      2014 Annual Research Report
  • [Book] Handbook of Metalloproteins to the Encyclopedia of Inorganic and Bioinorganic Chemistry2015

    • Author(s)
      Nobutaka Fujieda and Shinobu Itoh
    • Total Pages
      500
    • Publisher
      John Wiley & Sons
    • Related Report
      2014 Annual Research Report
  • [Book] Copper-Oxygen Chemistry2011

    • Author(s)
      S.Itoh, K.D.Kalrin
    • Total Pages
      462
    • Publisher
      John Wiley & Sons, Inc.
    • Related Report
      2010 Annual Research Report
  • [Remarks] BFC Lab

    • URL

      http://www-bfc.mls.eng.osaka-u.ac.jp/BioFunctional_Chemistry/Home.html

    • Related Report
      2014 Annual Research Report
  • [Remarks] BFC Lab

    • URL

      http://www-bfc.mls.eng.osaka-u.ac.jp/BioFunctional_Chemistry/Home.html

    • Related Report
      2011 Annual Research Report
  • [Remarks]

    • Related Report
      2010 Annual Research Report

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Published: 2010-08-23   Modified: 2019-07-29  

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