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A01 Hiroshi Fujii

Hiroshi Fujii

Participating A01

Affiliation

Faculty of Science, Nara Women’s University

Position

Professor

Contact

fujii@scc.nara-wu.ac.jp

HP

http://www.chem.nara-wu.ac.jp/~fujii/index.html

Research Project

Molecular mechanism

Abstract

Jacobsen catalysts are chiral salen metal complexes and have been known one of the most excellent asymmetric catalysts.  Jacobsen catalysts had been believed to have chiral distorted conformation of the salen ligand because of their high enatioselectivity.  However, x-ray crystal analysis revealed that Jacobsen catalysts have almost flat conformation of the salen ligand.  Therefore, there have not yet clarified what is the reactive intermediates of the reaction and how Jacobsen catalysts induce high enantioselectivity.  Recently, we found that Jacobsen catalysts show the chiral conformational change of the salen ligand when central metal is oxidized and strong axial ligands bind to the metal center.  In this project, we will study the mechanism of the chiral conformational change of the salen ligand.

Research Areas

Bioinorganic Chemistry、Magnetic Resonance, Inorganic Chemistry

Keywords

Asymmetric oxidation, Reactive intermediate, Metal-oxo, Terminal oxidant adduct, Salen

2020

[18] Unique Electronic Structures of the Highly Ruffled Hemes in Heme-Degrading Enzymes of Staphylococcus aureus, IsdG and IsdI, by Resonance Raman and Electron Paramagnetic Resonance Spectroscopies,
Satoshi Takahashi; Shusuke Nambu; Toshitaka Matsui; Hiroshi Fujii; Haruto Ishikawa; Yasuhisa Mizutani; Kouhei Tsumoto; Masao Ikeda-Saito, Biochemistry, 3918 - 3928, 2020
DOI: 10.1021/acs.biochem.0c00731.
[17] Photo-biohydrogen Production by Photosensitization with Biologically Precipitated Cadmium Sulfide in Hydrogen-Forming Recombinant Escherichia coli,
Yuki Honda; Yuka Shinohara; Motonori Watanabe; Tatsumi Ishihara; Hiroshi Fujii , ChemBioChem., 21, 3389 - 3397, 2020
DOI: 10.1002/cbic.202000385.
[16] Visible light-driven, external mediator-free H2 production by a combination of a photosensitizer and a whole-cell biocatalyst: Escherichia coli expressing [FeFe]-hydrogenase and muturase genes,
Yuki Honda; Yuka Shimonhara; Hiroshi Fujii, Catalysis Science & Technology, 10, 6006 - 6012, 2020
DOI: 10.1039/D0CY01099E.
[15] DFT insight into axial ligand effects on electronic structure and mechanistic reactivity of oxoiron(IV) porphyrin,
Zhifeng Ma; Naoki Nakatani; Hiroshi Fujii; Masahiko Hada, Phys. Chem. Chem Phys., 22, 12173 - 12179, 2020
DOI: 10.1039/D0CP01867H.
[14] Spectroscopic Evidence for Acid-Catalyzed Disproportionation Reaction of Oxoiron(IV) Porphyrin to Oxoiron(IV) Porphyrin π-Cation Radical and Iron(III) Porphyrin,
Kana Nishikawa; Yuki Honda; Hiroshi Fujii, J. Am. Chem. Soc., 142, 4980 - 4984, 2020
DOI: 10.1021/jacs.9b13503 .
[13] Effect of External Electric Fields on the Oxidation Reaction of Olefins by Fe(IV)OCl­Porphyrin Complexes,
Zhifeng Ma; Naoki Nakatani; Hiroshi Fujii; Masahiko Hada, Bull. Chem. Soc. Jpn., 93, 187 - 193, 2020
DOI: 10.1246/bcsj.20190293.

2019

[12] Small Reorganization Energy for Ligand-Centered Electron-Transfer Reduction of Compound I to Compound II in Heme Model Study,
Nami Fukui; Xiao-Xi Li ; Wonwoo Nam ; Shunichi Fukuzumi; Hiroshi Fujii , Inorg. Chem., 58, 8263 - 8266, 2019
DOI: 10.1021/acs.inorgchem.9b01051.
[11] Direct Observation of Primary C–H Bond Oxidation by An Oxido-iron(IV) Porphyrin π-Radical Cation Complex in a Fluorinated Carbon Solvent,
Yuma Morimoto; Yuki, Shimaoka; Yuri, Ishimizu; Hiroshi Fujii; Shinobu Itoh, Angew. Chem. Int. Ed., 58, 10863 - 10866, 2019
DOI: 10.1002/anie.201901608.
[10] Experimental and Theoretical Studies of the Porphyrin Ligand Effect on the Electronic Structure and Reactivity of Oxoiron(IV) porphyrin π-Cation Radical Complexes,
Yuri Ishimizu; Zhifeng Ma; Masahiko Hada; Hiroshi Fujii, J. Biol. Inorg. Chem., 24, 483 - 494, 2019
DOI: 10.1007/s00775-019-01664-3.
[9] Site-Selective Supramolecular Complexation Activates Catalytic Ethane-Oxidation of m-Nitrido-Bridged Iron Porphyrinoid Dimer,
Yasuyuki Yamada; Nozomi Mihara; Hikaru Takaya; Yasutaka Kitagawa; Kazunobu Igawa; Katsuhiko Tomooka ; Hiroshi Fujii; Kentaro Tanaka , Chem. Eur. J., 25, 3369 - 3375, 2019
DOI: 10.1002/chem.201805580.
[8] Substitution Effects on Olefin Epoxidation Catalyzed by Oxoiron(IV) Porphyrin π-Cation Radical Complexes: A DFT Study,
Zhifeng Ma; Kasumi Ukaji; Naoki Nakatani; Hiroshi Fujii; Masahiko Hada, J. Cmput. Chem., 40, 1780 - 1788, 2019
DOI: 10.1002/jcc.25831.

2018

[7] Preparation, Characterization and Reactivity of a Bis-Hypochlorite Adduct of a Chiral Manganese(IV)-Salen Complex,
kuko Araki; Kaoru Fukui; Hiroshi Fujii, Inorg. Chem., 57, 1685 - 1688, 2018.
[6] Critical Factors in Determining the Heterolytic versus Homolytic Bond Cleavage of Terminal Oxidants by Iron(III) Porphyrin Complexes,
Sawako Yokota; Hiroshi Fujii, J. Am. Chem. Soc., 140, 5127 - 5137, 2018.
[5] Coexpression of 5-aminolevulinic Acid Synthase Gene Facilitates Heterologous Production of Thermostable Cytochrome P450, CYP119, in Holo Form in Escherichia coli,
Yuki Honda; Ki Nanasawa; Hiroshi Fujii, ChemBioChem, 19, 2156 - 2159, 2018.

2016

[4] The Origin of Relative Stability of Di-μ-oxo M-M Chiral Salen Complexes [M-M = Ti (IV)-Ti(IV), V(IV)-V(IV), Cr(IV)-Cr(IV) and Mn(IV)-Mn(IV)]: A Quantum-Chemical Analysis,
Radhika Narayanan; Archana Velloth; Takuya Kurahashi; Hiroshi Fujii; Masahiko Hada, Bull. Chem. Soc. Jpn., 89, 447 - 454, 2016.
[3] Participation of Electron-Transfer Process in Rate-Limiting Step of Aromatic Hydroxylation Reactions by Compound I Models of Heme Enzyme,
Maaya Asaka; Hiroshi Fujii, J. Am. Chem. Soc., 138, 8048 - 8051, 2016.
[2] The Functional Role of the structure of the Dioxo-isobacteriochlorin Structure in the Catalytic Site of Cytochrome cd1 for the Reduction of Nitrite,
Hiroshi Fujii; Daisuke Yamaki; Takashi Ogura; Masahiko Hada, Chem. Sci., 7, 2896 - 2906, 2016.
[1] Unique coupling of mono- and dioxygenase chemistries in a single active site promotes heme degradation,
Toshitaka Matsui; Shusuke Nambu; Celia W. Goulding; Satoshi Takahashi; Hiroshi Fujii; Masao Ikeda- Saito, Proc. Natl. Acad. Sci. USA, 113, 3779 - 3784, 2016.