Site-Selective C–H Bond Oxidation Catalyzed by Mononuclear Nonheme Iron Complexes: Additive Effects of Carboxylic Acids

Yutaka Hitomi
Doshisha University
Nov. 30 16:45~17:10


Development of selective C−H oxidation catalysts under mild conditions is strongly desired because of the application for the synthesis of complicated organic compounds. A possible approach to this purpose is to mimic biological systems, because some enzymes are capable such reactions under very mild conditions. Inspired by metalloenzymes, various iron catalysts have been developed. Especially, iron complexes having two cis-oriented labile coordination sites show relatively high 3°/2° ratios in the oxidation of adamantane with hydrogen peroxide. For example, Fe(II)tpa and Fe(II)Pytacn show the selectivity with 3°/2° of 17 and 30, respectively (Fig. 1).1,2 In addition, recent studies have revealed that the activity of mononuclear iron complex was improved by the addition of acetic acid.3 We reported a new class of selective iron-based catalysts, Fe(III)complexes supported by pentadentate carboxamido ligands, Fe(III)dpaq, which afforded high 3°/2° ratio reaching 29 (Fig. 1).4,5 In this presentation, we will report on highly selective alkane hydroxylation catalyzed by a new iron(III) complex supported by a tetradentate carboxamido ligand, Fe(III)propaq, in the presence of acids.

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  1. Costas, M.; Chen, K.; Que, L., Jr. Coord. Chem. Rev. 2000, 200-202, 517.
  2. Company, A.; Gómez, L.; Güell, M.; Ribas, X.; Luis, J. M.; Que, L., Jr., Costas M. J. Am. Chem. Soc. 2007, 129, 15766.
  3. Chen, M. S.; White, M. C. Science, 2007, 318, 738.
  4. Hitomi, Y.; Arakawa, K.; Funabiki, T.; Kodera, M. “An Iron(III) Monoamidate Complex Catalyst for Selective Hydroxylation of Alkane C–H Bonds with Hydrogen Peroxide” Angew. Chem. Int. Ed., 2012, 51, 3448.
  5. Hitomi, Y.; Arakawa, K.; Kodera, M. “Electronic Tuning of Iron-Oxo Mediated C-H Activation: Effect of Electron Donating Ligand on Selectivity” Chem. Eur. J. 2013, 19, 14697.
  6. Hitomi, Y.; Arakawa. K.; Kodera, M. “Synthesis, Stability and Reactivity of the First Mononuclear Nonheme Oxoiron(IV) Species with Monoamido Ligation: A Putative Reactive Species Generated from Iron-Bleomycin” Chem. Commun. 2014, 50, 7485.


  • 1996-1999, Ph.D. Kyoto University
  • 1994-1996, M.S. Kyoto University
  • 1990-1994, B.S. Kyoto University


Professional Career

  • 2017-Present, JST PREST Researcher (Concurrent Post)
  • 2014-Present, Professor, Doshisha University
  • 2008-2014, Associate Professor, Doshisha University
  • 2007-2008, Lecturer in Chemistry, Kyoto University
  • 2001-2007, Assistant Professor, Kyoto University
  • 1999-2001, Postdoctoral Fellow, Northwestern University (Thomas O’Halloran Lab)
  • 1999-2000, JSPS Researcher Fellow (PD)
  • 1996-1999, JSPS Researcher Fellow (DC1)


Awards and Honors

  • 2016, Nagase Foundation Award
  • 2008, Bio-related Chemistry Symposium Lecture Award