ITO, Hajime

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ITO, Hajime
Principal Investigator, Vice Director, Professor
Hokkaido University
Research Areas
Organic Synthetic Chemistry, Organoelement Chemistry, Mechanochemistry
Related Website

hajito atmark

ITO, Hajime Group
Principal Investigator
  • thumbnail image
    ITO, Hajime
Faculty Members
Postdoctoral Fellows
Research Collaborators
  • KUBO, Shotaro

About the Research

Research Theme

Development of new reactions of small molecules with various elements


Development of New Reactions, Mechano-Responsive Materials, Mechanochemical Synthesis
Research Outline

Our research group has three main topics. The first is the development of new reactions for organic synthesis using copper, boron, and other organo-metallic compounds. The second is the development of new materials that show interesting optical properties in response to mechanical stress such as grinding. And the third topic is mechano-chemical synthesis. This solvent-free approach promises to be more efficient and environmentally friendly than current light-activated reaction mechanisms.

Calculations constitute an increasingly important technology for the development of new chemical reactions, because experimental chemists have so far relied mainly on experimental screening or serendipity. But computational methods, especially the AFIR method, can predict new reactions and thus guide our search.

For details on MANABIYA course topics, please follow this link. To learn more about MANABIYA in general, please click here.

The Researcher’s Perspective

Whenever we come across an interesting, new phenomenon, we develop new projects. This is to the benefit of our students, who within their studies can successfully complete sometimes several projects. I am very lucky to be surrounded by excellent colleagues, so we are discovering many exciting things every day!

Representative Research Achievements

  • Reversible Mechanochromic Luminescence of (C6F5Au)2(μ-1,4-diisocyanobenzene)
    H. Ito, T. Saito, N. Oshima, N. Kitamura, S. Ishizaka, Y. Hinatsu, M. Wakeshima, M. Kato, K. Tsuge, M. Sawamura, J. Am. Chem. Soc., 2008, 130, 10044–10045
    DOI : 10.1021/ja8019356
  • A Screening Approach for the Discovery of Mechanochromic Gold(I) Isocyanide Complexes with Crystal-to-Crystal Phase Transitions
    T. Seki, Y. Takamatsu, H. Ito, J. Am. Chem. Soc., 2016, 138, 6252–6260
    DOI : 10.1021/jacs.6b02409
  • Mechanochromic Luminescence Based on Crystal-to-Crystal Transformation Mediated by a Transient Amorphous State
    S. Yagai, T. Seki, H. Aonuma, K. Kawaguchi, T. Karatsu, T. Okura, A. Sakon, H. Uekusa, H. Ito, Chem. Mater., 2016, 28, 234–241
    DOI : 10.1021/acs.chemmater.5b03932
  • Boration of an α,β-enone Using a Diboron Promoted by a Copper(I)-Phosphine Mixture Catalyst
    H. Ito, H. Yamanaka, J. Tateiwa, A. Hosomi, Tetrahedron Lett., 2000, 41, 6821–6825
    DOI : 10.1021/om800946k
  • Copper-Catalyzed Enantioselective Substitution of Allylic Carbonates with Diboron: An Efficient Route to Optically Active alpha-Chiral Allylboronates
    H. Ito, S. Ito, Y. Sasaki, K. Matsuura, M. Sawamura, J. Am. Chem. Soc., 2007, 129, 14856–14857
    DOI : 10.1021/ja076634o

Related Research



  • Cu(I)-Catalyzed Enantioselective Gamma-Boryl Substitution of Trifluoromethyl- and Silyl-Substituted Alkenes
    N. Oyama, S. Akiyama, K. Kubota, T. Imamoto, H. Ito, European Journal of Organic Chemistry, 2022, 2022,
    DOI: 10.1002/ejoc.202200664
  • Solid-State Cross-Coupling Reactions of Insoluble Aryl Halides under Polymer-Assisted Grinding Conditions
    K. Kubota, T. Seo, H. Ito, Faraday Discussions, 2022, ,
    DOI: 10.1039/d2fd00121g
  • Mechanochemically Generated Calcium-Based Heavy Grignard Reagents and Their Application to Carbon-Carbon Bond-Forming Reactions
    P. Gao, J. L. Jiang, S. Maeda, K. Kubota, H. Ito, Angew. Chem., Int. Ed., 2022, ,
    DOI: 10.1002/anie.202207118
  • Mechanical Deformation and Multiple Thermal Restoration of Organic Crystals: Reversible Multi-Stage Shape-Changing Effect with Luminescence-Color Changes
    C. Feng, T. Seki, S. Sakamoto, T. Sasaki, S. Takamizawa, H. Ito, Chem. Sci., 2022, 13, 9544-9551
    DOI: 10.1039/d2sc03414j
  • Palladium-Catalyzed Solid-State Borylation of Aryl Halides Using Mechanochemistry
    K. Kubota, E. Baba, T. Seo, T. Ishiyama, H. Ito, Beilstein Journal of Organic Chemistry, 2022, 18, 855-862
    DOI: 10.3762/bjoc.18.86
  • Conformationally Fixed Chiral Bisphosphine Ligands by Steric Modulators on the Ligand Backbone: Selective Synthesis of Strained 1,2-Disubstituted Chiral Cis-Cyclopropanes
    H. Iwamoto, Y. Ozawa, Y. Hayashi, T. Imamoto, H. Ito, J. Am. Chem. Soc., 2022, 144, 10483-10494
    DOI: 10.1021/jacs.2c02745
  • Insight into the Reactivity Profile of Solid-State Aryl Bromides in Suzuki-Miyaura Cross-Coupling Reactions Using Ball Milling
    K. Kubota, K. Kondo, T. Seo, H. Ito, Synlett, 2022, 33, 898-902
    DOI: 10.1055/a-1748-3797
  • Solid-State Luminescence of Au(I) Complexes with External Stimuli-Responsive Properties
    M. Jin, H. Ito, Journal of Photochemistry and Photobiology C-Photochemistry Reviews, 2022, 51,
    DOI: 10.1016/j.jphotochemrev.2021.100478


  • Palladium-Catalyzed Solid-State Polyfluoroarylation of Aryl Halides Using Mechanochemistry
    R. Takahashi, T. Seo, K. Kubota, H. Ito, Acs Catalysis, 2021, 11, 14803-14810
    DOI: 10.1021/acscatal.1c03731
  • Efficient Access to Materials-Oriented Aromatic Alkynes via the Mechanochemical Sonogashira Coupling of Solid Aryl Halides with Large Polycyclic Conjugated Systems
    Y. P. Gao, C. Feng, T. Seo, K. Kubota, H. Ito, Chem. Sci., 2021, 13, 430-438
    DOI: 10.1039/d1sc05257h
  • Distinct Fold-Mode Formation of Crystalline Cu(I) Helical Coordination Polymers with Alternation of the Solid-State Emission Using Shape of the Counter Anions
    M. Jin, R. Ando, H. Ito, Inorg. Chem., 2021, 61, 3-9
    DOI: 10.1021/acs.inorgchem.1c02725
  • Solid-State C-N Cross-Coupling Reactions with Carbazoles as Nitrogen Nucleophiles Using Mechanochemistry
    K. Kubota, T. Endo, M. Uesugi, Y. Hayashi, H. Ito, ChemSusChem, 2021, 15,
    DOI: 10.1002/cssc.202102132
  • Mechanochemical Synthesis of Magnesium-Based Carbon Nucleophiles in Air and Their Use in Organic Synthesis
    R. Takahashi, A. Q. Hu, P. Gao, Y. P. Gao, Y. D. Pang, T. Seo, J. L. Jiang, S. Maeda, H. Takaya, K. Kubota, H. Ito, Nat. Commun., 2021, 12,
    DOI: 10.1038/s41467-021-26962-w
  • Regio- and Stereoselective Synthesis of Multi-Alkylated Allylic Boronates through Three-Component Coupling Reactions between Allenes, Alkyl Halides, and a Diboron Reagent
    Y. Ozawa, K. Endo, H. Ito, J. Am. Chem. Soc., 2021, 143, 13865-13877
    DOI: 10.1021/jacs.1c06538
  • Charge-Transfer Crystal with Segregated Packing Structure Constructed with Hexaarylbenzene and Tetracyanoquinodimethane
    R. Ando, M. Jin, H. Ito, Crystengcomm, 2021, 23, 5564-5568
    DOI: 10.1039/d1ce00726b
  • Synthesis of Hydrosilylboronates via the Monoborylation of a Dihydrosilane Si-H Bond and Their Application for the Generation of Dialkylhydrosilyl Anions
    T. Takeuchi, R. Shishido, K. Kubota, H. Ito, Chem. Sci., 2021, 12, 11799-11804
    DOI: 10.1039/d1sc01440d
  • Development of Selective Reactions Using Ball Milling
    K. Kubota, H. Ito, J. Syn. Org. Chem. Jpn., 2021, 79, 492-502
  • Introduction of a Luminophore into Generic Polymers via Mechanoradical Coupling with a Prefluorescent Reagent
    K. Kubota, N. Toyoshima, D. Miura, J. L. Jiang, S. Maeda, M. Jin, H. Ito, Angew. Chem., Int. Ed., 2021, 60, 16003-16008
    DOI: 10.1002/anie.202105381
  • Synthesis of Chiral Alpha-Amino Tertiary Boronates via the Catalytic Enantioselective Nucleophilic Borylation of Dialkyl Ketimines
    K. Kubota, D. Miura, T. Takeuchi, S. Osaki, H. Ito, Acs Catalysis, 2021, 11, 6733-6740
    DOI: 10.1021/acscatal.1c01689
  • Synthesis and Optical Properties of C,N-Swapped Boranils Derived from Potassium Acyltrifluoroborates
    S. Matsuura, J. Taguchi, T. Seki, H. Ito, Bulletin of the Chemical Society of Japan, 2021, 94, 1547-1552
    DOI: 10.1246/bcsj.20210024
  • Backbone-Modified C-2-Symmetrical Chiral Bisphosphine TMSQuinoxP*: Asymmetric Borylation of Racemic Allyl Electrophiles
    H. Iwamoto, Y. Ozawa, Y. Takenouchi, T. Imamoto, H. Ito, J. Am. Chem. Soc., 2021, 143, 6413-6422
    DOI: 10.1021/jacs.0c08899
  • (9-Isocyanoanthracene)gold(I) Complexes Exhibiting Two Modes of Crystal Jumps by Different Structure Change Mechanisms
    K. Kato, T. Seki, H. Ito, Inorg. Chem., 2021, 60, 10849-10856
    DOI: 10.1021/acs.inorgchem.1c00881
  • A Copper(I)-Catalyzed Radical-Relay Reaction Enabling the Intermolecular 1,2-Alkylborylation of Unactivated Olefins
    S. Akiyama, N. Oyama, T. Endo, K. Kubota, H. Ito, J. Am. Chem. Soc., 2021, 143, 5260-5268
    DOI: 10.1021/jacs.1c02050
  • Tackling Solubility Issues in Organic Synthesis: Solid-State Cross-Coupling of Insoluble Aryl Halides
    T. Seo, N. Toyoshima, K. Kubota, H. Ito, J. Am. Chem. Soc., 2021, 143, 6165-6175
    DOI: 10.1021/jacs.1c00906
  • Copper(I)-Catalyzed Stereoselective Silylative Dearomatization of Indoles and Pyrroles Using Silylboronates
    K. Hayama, R. Takahashi, K. Kubota, H. Ito, Chem. Lett., 2021, 50, 289-292
    DOI: 10.1246/cl.200725
  • Encapsulating N-Heterocyclic Carbene Binuclear Transition-Metal Complexes as a New Platform for Molecular Rotation in Crystalline Solid-State
    M. Jin, R. Ando, M. J. Jellen, M. A. Garcia-Garibay, H. Ito, J. Am. Chem. Soc., 2021, 143, 1144-1153
    DOI: 10.1021/jacs.0c11981


  • Synthesis of Chiral N-Heterocyclic Allylboronates via the Enantioselective Borylative Dearomatization of Pyrroles
    K. Hayama, R. Kojima, K. Kubota, H. Ito, Org. Lett., 2020, 22, 739-744
    DOI: 10.1021/acs.orglett.9b04581
  • Aurophilicity-Mediated Construction of Emissive Porous Molecular Crystals as Versatile Hosts for Liquid and Solid Guests
    T. Seki, K. Ida, H. Sato, S. Aono, S. Sakaki, H. Ito, Chem. Eur. J., 2020, 26, 735-744
    DOI: 10.1002/chem.201904597
  • Synthesis and Tunable Optical Properties of C,N-Chelated Borate Luminophores Derived from Potassium Acyltrifluoroborates
    J. Taguchi, S. Matsuura, T. Seki, H. Ito, Chem. Eur. J., 2020, 26, 2450-2455
    DOI: 10.1002/chem.201904983
  • Air- and Moisture-Stable Xantphos-Ligated Palladium Dialkyl Complex as a Precatalyst for Cross-Coupling Reactions
    R. Takahashi, K. Kubota, H. Ito, Chem. Commun., 2020, 56, 407-410
    DOI: 10.1039/c9cc06946a
  • Mechanochemical Cross-Coupling Reactions
    K. Kubota, H. Ito, Trends in Chemistry, 2020, 2, 1066-1081
    DOI: 10.1016/j.trechm.2020.09.006
  • Solid-State Radical C-H Trifluoromethylation Reactions Using Ball Milling and Piezoelectric Materials
    Y. D. Pang, J. W. Lee, K. Kubota, H. Ito, Angew. Chem., Int. Ed., 2020, 59, 22570-22576
    DOI: 10.1002/anie.202009844
  • A Glove-Box- and Schlenk-Line-Free Protocol for Solid-State C-N Cross-Coupling Reactions Using Mechanochemistry
    K. Kubota, R. Takahashi, M. Uesugi, H. Ito, Acs Sustainable Chemistry & Engineering, 2020, 8, 16577-16582
    DOI: 10.1021/acssuschemeng.0c05834
  • General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis
    R. Shishido, M. Uesugi, R. Takahashi, T. Mita, T. Ishiyama, K. Kubota, H. Ito, J. Am. Chem. Soc., 2020, 142, 14125-14133
    DOI: 10.1021/jacs.0c03011
  • Thermosalience in Macrocycle-Based Soft Crystals via Anisotropic Deformation of Disilanyl Architecture
    K. Omoto, T. Nakae, M. Nishio, Y. Yamanoi, H. Kasai, E. Nishibori, T. Mashimo, T. Seki, H. Ito, K. Nakamura, N. Kobayashi, N. Nakayama, H. Goto, H. Nishihara, J. Am. Chem. Soc., 2020, 142, 12651-12657
    DOI: 10.1021/jacs.0c03643
  • Photoluminescent Ferroelastic Molecular Crystals
    T. Seki, C. Feng, K. Kashiyama, S. Sakamoto, Y. Takasaki, T. Sasaki, S. Takamizawa, H. Ito, Angew. Chem., Int. Ed., 2020, 59, 8839-8843
    DOI: 10.1002/anie.201914610
  • Selective Mechanochemical Monoarylation of Unbiased Dibromoarenes by in Situ Crystallization
    T. Seo, K. Kubota, H. Ito, J. Am. Chem. Soc., 2020, 142, 9884-9889
    DOI: 10.1021/jacs.0c01739
  • Copper(I)-Catalyzed Boryl Substitution of 1-Trifluoromethyl Allenes for the Synthesis of 3-Boryl-Substituted 1,1-Gem-Difluorodienes
    S. Akiyama, S. Nomura, K. Kubota, H. Ito, J. Org. Chem., 2020, 85, 4172-4181
    DOI: 10.1021/acs.joc.9b03353
  • Silyl-Group-Directed Linear-Selective Allylation of Carbonyl Compounds with Trisubstituted Allylboronates Using a Copper(I) Catalyst
    H. Iwamoto, Y. Hayashi, Y. Ozawa, H. Ito, Acs Catalysis, 2020, 10, 2471-2476
    DOI: 10.1021/acscatal.9b05408
  • Crystal Jumping of Simple Hydrocarbons: Cooling-Induced Salient Effect of Bis-, Tri-, and Tetraphenylethene through Anisotropic Lattice Dimension Changes Without Thermal Phase Transitions
    T. Seki, T. Mashimo, H. Ito, Chem. Lett., 2020, 49, 174-177
    DOI: 10.1246/cl.190768
  • Mixed Crystal Formation of Two Gold Isocyanide Complexes with Various Ratios for Continuous Tuning of Photophysical Properties
    T. Seki, N. Toyoshima, H. Ito, Dalton Trans., 2020, 49, 2073-2076
    DOI: 10.1039/d0dt00195c
  • Stacked Nanocarbon Photosensitizer for Efficient Blue Light Excited Eu(III) Emission
    Y. Kitagawa, F. Suzue, T. Nakanishi, K. Fushimi, T. Seki, H. Ito, Y. Hasegawa, Communications Chemistry, 2020, 3, 7
    DOI: 10.1038/s42004-019-0251-z


  • Catalytic Enantioselective Synthesis of Allylic Boronates Bearing a Trisubstituted Alkenyl Fluoride and Related Derivatives
    Akiyama, S, Kubota, K, Mikus, MS, Paioti, PHS, Romiti, F, Liu, QH, Zhou, YB, Hoveyda, AH, H. Ito, Angew. Chem., Int. Ed., 2019, 58, 11998-12003
    DOI: 10.1002/anie.201906283
  • Dependence of Absorption and Emission Spectra on Polymorphs of Gold(I) Isocyanide Complexes: Theoretical Study with QM/MM Approach
    S. Aono, T. Seki, H. Ito, S. Sakaki, J. Phys. Chem. C, 2019, 123, 4773-4794
    DOI: 10.1021/acs.jpcc.8b10602
  • Near-IR Luminescent YbIII Coordination Polymers Composed of Pyrene Derivatives for Thermostable Oxygen Sensors
    Y. Hasegawa, T. Matsui, Y. Kitagawa, T. Nakanishi, T. Seki, H. Ito, Y. Nakasaka, T. Masuda, K. Fushimi, Chem. Eur. J., 2019, 25, 12308-12315
    DOI: 10.1002/chem.201902583
  • Microphase Separation of Carbohydrate-Based Star-Block Copolymers with Sub-10 nm Periodicity
    T. Isono, N. Kawakami, K. Watanabe, K. Yoshida, I. Otsuka, H. Mamiya, H. Ito, T. Yamamoto, K. Tajima, R. Borsali, T. Satoh, Polym. Chem., 2019, 10, 1119-1129
    DOI: 10.1039/c8py01745j
  • Copper(I)-Catalyzed Enantioconvergent Borylation of Racemic Benzyl Chlorides Enabled by Quadrant-by-Quadrant Structure Modification of Chiral Bisphosphine Ligands
    H. Iwamoto, K. Endo, Y. Ozawa, Y. Watanabe, K. Kubota, T. Imamoto, H. Ito, Angew. Chem., Int. Ed., 2019, 58, 11112-11117
    DOI: 10.1002/anie.201906011
  • Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals
    M. Jin, S. Yamamoto, T. Seki, H. Ito, MA. Garcia-Garibay, Angew. Chem., Int. Ed., 2019, 58, 18003-18010
    DOI: 10.1002/anie.201909048
  • Redox Reactions of Small Organic Molecules Using Ball Milling and Piezoelectric Materials
    K. Kubota, YD. Pang, A. Miura, H. Ito, Science, 2019, 366, 1500-1504
    DOI: 10.1126/science.aay8224
  • Olefin-Accelerated Solid-State C-N Cross-Coupling Reactions Using Mechanochemistry
    K. Kubota, T. Seo, K. Koide, Y. Hasegawa, H. Ito, Nat. Commun., 2019, 10,
    DOI: 10.1038/s41467-018-08017-9
  • Mechanochemistry Allows Carrying out Sensitive Organometallic Reactions in Air: Glove-Box-and-Schlenk-Line-Free Synthesis of Oxidative Addition Complexes from Aryl Halides and Palladium(0)
    K. Kubota, R. Takahashi, H. Ito, Chem. Sci., 2019, 10, 5837-5842
    DOI: 10.1039/c9sc01711a
  • Synthesis of 2-Alkyl-2-Boryl-Substituted-Tetrahydrofurans via Copper(I)-Catalysed Borylative Cyclization of Aliphatic Ketones
    K. Kubota, M. Uesugi, S. Osaki, H. Ito, Org. Biomol. Chem., 2019, 17, 5680-5683
    DOI: 10.1039/c9ob00962k
  • Iridium(I)-Catalyzed C-H Borylation in Air by Using Mechanochemistry
    YD. Pang, T. Ishiyama, K. Kubota, H. Ito, Chem. Eur. J., 2019, 25, 4654-4659
    DOI: 10.1002/chem.201900685
  • Luminescent Mechanochromism of Gold N-Heterocyclic Carbene Complexes with Hypso- and Bathochromic Spectral Shifts
    T. Seki, K. Kashiyama, H. Ito, Dalton Trans., 2019, 48, 7105-7109
    DOI: 10.1039/c9dt00566h
  • Anisotropic Strain Release in a Thermosalient Crystal: Correlation Between the Microscopic Orientation of Molecular Rearrangements and the Macroscopic Mechanical Motion
    T. Seki, T. Mashimo, H. Ito, Chem. Sci., 2019, 10, 4185-4191
    DOI: 10.1039/c8sc05563g
  • Solid-State Suzuki-Miyaura Cross-Coupling Reactions: Olefin-Accelerated C-C Coupling Using Mechanochemistry
    T. Seo, T. Ishiyama, K. Kubota, H. Ito, Chem. Sci., 2019, 10, 8202-8210
    DOI: 10.1039/c9sc02185j
  • Concise Synthesis of Potassium Acyltrifluoroborates from Aldehydes Through Copper(I)-Catalyzed Borylation/Oxidation
    J. Taguchi, T. Takeuchi, R. Takahashi, F. Masero, H. Ito, Angew. Chem., Int. Ed., 2019, 58, 7299-7303
    DOI: 10.1002/anie.201901748


  • Synthesis of Acylborons by Ozonolysis of Alkenylboronates: Preparation of an Enantioenriched Amino-Acid Acylboronate
    J. Taguchi, T. Ikeda, R. Takahashi, I. Sasaki, Y. Ogasawara, T. Dairi, N. Kato, Y. Yamamoto, JW. Bode, H. Ito, Angew. Chem., Int. Ed., 2017, 56, 13847-13851
    DOI: 10.1002/anie.201707933


  • Cationic Ir/Me-BIPAM-Catalyzed Asymmetric Intramolecular Direct Hydroarylation of α-Keto Amides
    T. Shirai, H. Ito, Y. Yamamoto, Angew. Chem., Int. Ed., 2014, 53, 2658-2661
    DOI: 10.1002/anie.201400147


  • Tetrabutylammonium 2-Pyridyltriolborate Salts for Suzuki-Miyaura Cross-Coupling Reactions with Aryl Chlorides
    S. Sakashita, M. Takizawa, J. Sugai, H. Ito, Y. Yamamoto, Org. Lett., 2013, 15, 4308-4311
    DOI: 10.1021/ol402268g
  • Cross-Coupling Reaction with Lithium Methyltriolborate
    Y. Yamamoto, K. Ikizakura, H. Ito, N. Miyaura, Molecules, 2013, 18, 430-439
    DOI: 10.3390/molecules18010430


  • Me-BIPAM for the Synthesis of Optically Active 3-Aryl-3-Hydroxy-2-Oxindoles by Ruthenium-Catalyzed Addition of Arylboronic Acids to Isatins
    Y. Yamamoto, M. Yohda, T. Shirai, H. Ito, N. Miyaura, Chem. Asian J., 2012, 7, 2446-2449
    DOI: 10.1002/asia.201200481