• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Development of asymmetric addition reactions of E-H bond (E = main group elements) to unsaturated bonds catalyzed by an iron complex

Research Project

Project/Area Number 16K05728
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionOsaka City University

Principal Investigator

Itazaki Masumi  大阪市立大学, 大学院理学研究科, 講師 (60382032)

Co-Investigator(Kenkyū-buntansha) 中沢 浩  大阪市立大学, 大学院理学研究科, 特任教授 (00172297)
Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2017: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2016: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywords鉄 / ヒドロシリル化 / ヒドロホスフィン化 / 光学活性 / 鉄触媒 / キラル配位子 / ホスフィンカルボキシアミド / 不斉合成 / 触媒
Outline of Final Research Achievements

Previously, we found regioselective double-hydrophosphination reaction of terminal arylalkyne with secondary phosphine catalyzed by an iron methyl complex having a cyclopentadienyl ligand. Therefore, we synthesized new iron methyl complexes having chiral version of cyclopentadienyl ligands for asymmetric addition reaction. The iron complex showed the catalytic activity of regioselective double-hydrophosphination reaction. In addition, asymmetric hydrosilylation reaction of ketone was also achieved by using our catalytic system. However, the enantiomeric excess of obtained compounds in these reactions were not high.

Academic Significance and Societal Importance of the Research Achievements

光学活性化合物は、医薬品中間体、機能性材料のみならず、特にホスフィンの場合には遷移金属触媒を用いた不斉合成において欠かすことの出来ない配位子となる。しかし、これまでの合成法として、高価な貴金属を触媒に用いる反応は多く報告されているが、鉄などの安価な金属を触媒にした例はあまりないのが現状である。今回我々の見出した反応は生成物の光学純度は高くないものの、鉄触媒を用いて進行した例であり、今後の発展により有機金属化学などの学術的な面の貢献のみに留まらず、その波及効果は医薬品中間体や医薬品の安定供給、コストダウンおよび安全性の向上など工業的な観点からも見ても大きなものとなることが期待できる。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (30 results)

All 2019 2018 2017 2016

All Journal Article (10 results) (of which Peer Reviewed: 9 results,  Open Access: 1 results,  Acknowledgement Compliant: 4 results) Presentation (20 results) (of which Int'l Joint Research: 3 results,  Invited: 5 results)

  • [Journal Article] Dehydrogenative Sn‒E (E = S, Se) Bond Formation Catalyzed by an Iron Complex2019

    • Author(s)
      Masumi Itazaki, Yudai Ogawa, Wataru Nakamura, Hiroshi Nakazawa
    • Journal Title

      Heteroat. Chem.

      Volume: 29 Issue: 5-6 Pages: e21461

    • DOI

      10.1002/hc.21461

    • NAID

      120006776861

    • URL

      https://ocu-omu.repo.nii.ac.jp/records/2019878

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Selective Double Addition Reaction of an E-H Bond (E = Si, B) to a C≡N Triple Bond of Organonitriles2018

    • Author(s)
      Masumi Itazaki, Hiroshi Nakazawa
    • Journal Title

      Molecules

      Volume: 23 Issue: 11 Pages: 2769-2769

    • DOI

      10.3390/molecules23112769

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Dihydride Iron Complex Bearing a Silyl-Tethered Cyclopentadienyl Ligand2018

    • Author(s)
      Masahiro Kamitani, Yoshinori Nishiguchi, Masumi Itazaki, Hiroshi Nakazawa
    • Journal Title

      Bull. Chem. Soc. Jpn.

      Volume: 91 Issue: 4 Pages: 588-593

    • DOI

      10.1246/bcsj.20170403

    • NAID

      130006707636

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Syntheses, Structures, and Electrochemical Properties of Iron(II) and Ruthenium(IV)-Hydrido Complexes with Ferrocenylsilyl Ligand(s)2017

    • Author(s)
      Masumi Itazaki, Yuka Shigesato, Makiko Minakata, Sho Ishii, Akio Ichimura, Hirohi Nakazawa
    • Journal Title

      J. Organomet. Chem.

      Volume: 847 Pages: 251-257

    • DOI

      10.1016/j.jorganchem.2017.05.045

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Selective double hydroboration and dihydroborylsilylation of organonitriles by an iron-indium cooperative catalytic system2017

    • Author(s)
      Masaki Ito, Masumi Itazaki, Hiroshi Nakazawa
    • Journal Title

      Inorg. Chem.

      Volume: 56 Issue: 22 Pages: 13709-13714

    • DOI

      10.1021/acs.inorgchem.7b01369

    • NAID

      120006556217

    • URL

      https://ocu-omu.repo.nii.ac.jp/records/2019893

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] 選択的なかご状錯体の合成―これまでにない頂点構造をもつかご状錯体2017

    • Author(s)
      板崎真澄、伊藤昌輝、中沢 浩
    • Journal Title

      化学

      Volume: 72 Pages: 62-63

    • Related Report
      2017 Research-status Report
  • [Journal Article] R/X exchange reactions in cis-[M(R)2{P(X)(NMeCH2)2}2] (M = Pd, Pt), via a phosphenium intermediate2016

    • Author(s)
      M. Itazaki, N. Tsuchida, Y. Shigesato, K. Takano, H. Nakazawa
    • Journal Title

      Dalton Trans.

      Volume: 45 Issue: 48 Pages: 19216-19220

    • DOI

      10.1039/c6dt02314b

    • NAID

      120006376423

    • URL

      https://ocu-omu.repo.nii.ac.jp/records/2019796

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Hydrogenation of Chlorosilanes by NaBH_42016

    • Author(s)
      M. Ito, M. Itazaki, T. Abe. H. Nakazawa
    • Journal Title

      Chem. Lett.

      Volume: 45 Issue: 12 Pages: 1434-1436

    • DOI

      10.1246/cl.160808

    • NAID

      130005475731

    • URL

      https://ocu-omu.repo.nii.ac.jp/records/2019741

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Selective Double Hydrosilylation of Nitriles Catalyzed by an Iron Complex Containing Indium Trihalide2016

    • Author(s)
      M. Ito, M. Itazaki, H. Nakazawa
    • Journal Title

      ChemCatChem

      Volume: 8 Issue: 21 Pages: 3323-3325

    • DOI

      10.1002/cctc.201600940

    • NAID

      120006532430

    • URL

      https://ocu-omu.repo.nii.ac.jp/records/2019708

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Tetrahedral cage complex with planar vertices : selective synthesis of Pt_4L_6 cage complexes involving hydrogen bonds driven by halide binding2016

    • Author(s)
      M. Ito, M. Iseki, M. Itazaki, H. Nakazawa
    • Journal Title

      Chem. Commun.

      Volume: 52 Issue: 45 Pages: 7205-7208

    • DOI

      10.1039/c6cc01448h

    • NAID

      120006576128

    • URL

      https://ocu-omu.repo.nii.ac.jp/records/2019714

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Iron Complex Catalyzing Regioselective Synthesis of Vinylphosphines and Unsymmetric Diphosphines, and Reactivity of Intermediate Complexes2018

    • Author(s)
      M. Itazaki, S. Katsube, T. Nochida, H. Nakazawa
    • Organizer
      43rd International Conference on Coordination Chemistry (ICCC2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 鉄触媒を用いたダブルヒドロホスフィン化反応による四配位リン化合物の合成と反応性2018

    • Author(s)
      後田朋哉、板崎真澄、中沢 浩
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 簡便なホスフィンカルボキシアミドの合成2018

    • Author(s)
      板崎真澄、松谷崇生、中沢 浩
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] イソシアナートのヒドロホスフィン化を用いたホスフィンカルボキシアミドの合成2018

    • Author(s)
      松谷崇生、板崎真澄、森内敏之、中沢 浩
    • Organizer
      第8回CSJ化学フェスタ2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] 四座リン配位子を有する鉄触媒を用いたヒドロシランの重合反応2018

    • Author(s)
      土中陽介、板崎真澄、森内敏之、中沢 浩
    • Organizer
      第8回CSJ化学フェスタ2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] 複数の配位サイトを有するホスフィン化合物を用いた金(Ⅰ) 錯体の合成と性質2018

    • Author(s)
      小川雄大、板崎真澄、森内敏之、中沢 浩
    • Organizer
      第8回CSJ化学フェスタ2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] 鉄の特長を活かした有機合成反応の開発-典型元素-水素結合の炭素-炭素不飽和結合への選択的な付加-2017

    • Author(s)
      板崎真澄
    • Organizer
      ヘテロ原子部会平成 28 年度第 3 回懇話会
    • Place of Presentation
      大阪科学技術センター 大阪府大阪市
    • Year and Date
      2017-02-06
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] Iron-Catalyzed Selective Hydrophosphonation of Alkynes and Vinylphosphines2017

    • Author(s)
      H. Nakazawa, M.Itazaki, M. Kamitani
    • Organizer
      2.6th Latin American Symposium on Coordination and Organometallic Chemistry (SILQCOM2017)
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 鉄-インジウム錯体触媒を用いた有機ニトリル化合物への選択的ヒドロシリル化およびヒドロボリル化反応2017

    • Author(s)
      板崎真澄、伊藤昌輝、中沢 浩
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 不完全ダブルキュバン四核亜鉛(II)錯体の合成とその反応性2017

    • Author(s)
      板崎真澄、土橋由夏子、中沢 浩
    • Organizer
      第44回有機典型元素化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 低毒性な鉄を触媒とするリン化合物の新規合成法の創製2016

    • Author(s)
      板崎真澄
    • Organizer
      大阪府立大学・大阪市立大学ニューテクフェア2016
    • Place of Presentation
      大阪産業創造館 大阪府大阪市
    • Year and Date
      2016-12-06
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] 鉄メチル錯体を触媒前駆体とする様々な有機合成反応と、その中間体錯体の反応性2016

    • Author(s)
      板崎真澄
    • Organizer
      第55回錯体化学若手の会近畿地区勉強会
    • Place of Presentation
      奈良女子大学 奈良県奈良市
    • Year and Date
      2016-11-19
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] ハロゲン化インジウムを有する鉄錯体を触媒として用いた選択的ダブルヒドロシリル化、ダブルヒドロボリル化およびジヒドロシリルボリル化反応の開発2016

    • Author(s)
      伊藤昌輝、板崎真澄、中沢 浩
    • Organizer
      第6回CSJ化学フェスタ2016
    • Place of Presentation
      タワーホール船堀 東京都江戸川区
    • Year and Date
      2016-11-14
    • Related Report
      2016 Research-status Report
  • [Presentation] 鉄錯体触媒を用いたC≡C 三重結合への段階的なP-H結合付加反応2016

    • Author(s)
      板崎真澄、勝部伸哉、後田朋哉、中沢 浩
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学 西早稲田キャンパス 東京都新宿区
    • Year and Date
      2016-09-14
    • Related Report
      2016 Research-status Report
  • [Presentation] Syntheses of Cage-Ahaped Complexes with Platinum or Palladium Planar Vertices and Their Structures -Reactions of Dihalogeno Platium or Palladium Complexes with Phosphinecarboxyakide-2016

    • Author(s)
      Masaki Ito, Masato Iseki, Masumi Itazaki, Takuya Otani, Hiroshi Nakazawa
    • Organizer
      錯体化学会第66回討論会
    • Place of Presentation
      福岡大学 福岡県福岡市 七隈キャンパス
    • Year and Date
      2016-09-10
    • Related Report
      2016 Research-status Report
  • [Presentation] ハロゲン化インジウムを配位子とするルテニウム錯体の反応性2016

    • Author(s)
      板崎真澄、土橋由夏子、伊藤昌輝、中沢 浩
    • Organizer
      錯体化学会第66回討論会
    • Place of Presentation
      福岡大学 福岡県福岡市 七隈キャンパス
    • Year and Date
      2016-09-10
    • Related Report
      2016 Research-status Report
  • [Presentation] Regioselective Hydrophosphination Reaction of a C≡C Triple Bond Catalyzed by an Iron Complex and Isolation of Intermediate Complexes2016

    • Author(s)
      Masumi Itazaki
    • Organizer
      International Symposium on Pure & Applied Chemistry (ISPAC) 2016
    • Place of Presentation
      Kuching, Sarawak, Malaysia
    • Year and Date
      2016-08-15
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 平面四配位白金錯体を頂点構造とする白金四核かご状錯体 Pt4L6 の選択的合成2016

    • Author(s)
      伊藤昌輝、井関柾登、板崎真澄、中沢 浩
    • Organizer
      第14回ホスト・ゲスト化学シンポジウム
    • Place of Presentation
      高知城ホール 高知県高知市
    • Year and Date
      2016-06-04
    • Related Report
      2016 Research-status Report
  • [Presentation] 鉄錯体を触媒とする末端アルキンの位置選択的なヒドロチオ化反応とその立体選択性の考察2016

    • Author(s)
      後田朋哉、板崎真澄、勝部伸哉、中村 渉、中沢 浩
    • Organizer
      第5回JACI/GSCシンポジウム
    • Place of Presentation
      ANAクラウンプラザホテル神戸 兵庫県神戸市
    • Year and Date
      2016-06-02
    • Related Report
      2016 Research-status Report
  • [Presentation] 鉄錯体を触媒とする末端アルキンの段階的なヒドロホスフィン化を用いた非対称1,2-ビスホスフィノエタンの合成2016

    • Author(s)
      板崎真澄、勝部伸哉、神谷昌宏、中沢 浩
    • Organizer
      第5回JACI/GSCシンポジウム
    • Place of Presentation
      ANAクラウンプラザホテル神戸 兵庫県神戸市
    • Year and Date
      2016-06-02
    • Related Report
      2016 Research-status Report

URL: 

Published: 2016-04-21   Modified: 2020-03-30  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi