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Development of Catalytic Transformation Method of Clorosilanes via Si-Cl Bond Cleavage

Research Project

Project/Area Number 18H01986
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionNational Institute of Advanced Industrial Science and Technology

Principal Investigator

Nakajima Yumiko  国立研究開発法人産業技術総合研究所, 材料・化学領域, 研究チーム長 (80462711)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥17,420,000 (Direct Cost: ¥13,400,000、Indirect Cost: ¥4,020,000)
Fiscal Year 2020: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2019: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000)
Fiscal Year 2018: ¥8,190,000 (Direct Cost: ¥6,300,000、Indirect Cost: ¥1,890,000)
Keywordsクロロシラン / 遷移金属錯体触媒 / 結合切断 / シリコーン / 低原子価金属錯体 / クロスカップリング反応 / 有機ケイ素化合物 / ニッケル触媒 / 鉄錯体 / 不活性結合切断 / 四座PNNP配位子 / 錯体触媒
Outline of Final Research Achievements

This research aims at development of catalytic systems to produce organosilicon compounds from chlorosilanes as versatile and cheap silicon feedstocks. To this end, we also performed detailed mechanistic study on the key reaction step, oxidative addition of a strong Si-Cl bond, which has not been clarified academically. Through this study, silyl-Heck reaction was developed to achieve selective monoalkenylization of polychlorosilane using electron-rich nickel catalysts. A selective alkylation reaction of chlorosilane using highly versatile alkylaluminum as a coupling partner was also achieved by combination of nickel or palladium precursors with a phosphorus-based ligand. By using these reactions, it has become possible to efficiently synthesize various organochlorosilanes, which has been difficult to synthesize by conventional methods.

Academic Significance and Societal Importance of the Research Achievements

有機ケイ素化合物は有機合成における鍵中間体やシリコーン原料として重要な化合物である。有機ケイ素化合物の一般的な合成手法として、工業的直接法により安価かつ大量に供給可能なクロロシランと有機金属試薬との量論反応が知られるが、本手法は ①反応性の高い有機金属試薬を利用するため、導入する置換基の種類が限定的、②量論量の有機金属試薬を用いるため、多くの副生成物を生じる、といった問題点を抱える。したがって、クロロシランを原料として、様々な有機ケイ素化合物の合成を可能とする“触媒反応”の開発は、極めて重要な課題である。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (42 results)

All 2021 2020 2019 2018

All Journal Article (18 results) (of which Peer Reviewed: 18 results,  Open Access: 2 results) Presentation (24 results) (of which Int'l Joint Research: 7 results,  Invited: 10 results)

  • [Journal Article] Selective hydrosilylation of allyl chloride with trichlorosilane2021

    • Author(s)
      Inomata, K.; Naganawa, Y.; Wang, Z. A.; Sakamoto, K.; Matsumoto, K.; Sato, K.; *Nakajima, Y.
    • Journal Title

      Commun. Chem.

      Volume: X Issue: 1

    • DOI

      10.1038/s42004-021-00502-5

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Metal-ligand cooperation behaviour of Fe and Co complexes bearing a tetradentate phenanthroline-based PNNP ligand2021

    • Author(s)
      Nakajima Yumiko、Takeshita Tomohiro、Jheng Nai-Yuan
    • Journal Title

      Dalton Transactions

      Volume: X Issue: 22 Pages: 7532-7536

    • DOI

      10.1039/d1dt00476j

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium/Carboxylic Acid‐catalyzed Alkenylation of Furfural and its Derivatives Using Alkynes2020

    • Author(s)
      Minami Yasunori、Miyamoto Hitomi、Nakajima Yumiko
    • Journal Title

      ChemCatChem

      Volume: 13 Issue: 3 Pages: 855-858

    • DOI

      10.1002/cctc.202001685

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A General and Selective Synthesis of Methylmonochlorosilanes from Di-, Tri-, and Tetrachlorosilanes2020

    • Author(s)
      Naganawa Yuki、Sakamoto Kei、Nakajima Yumiko
    • Journal Title

      Organic Letters

      Volume: 23 Issue: 2 Pages: 601-606

    • DOI

      10.1021/acs.orglett.0c04175

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Co(I) complexes with a tetradentate phenanthroline-based PNNP ligand as a potent new metal?ligand cooperation platform2020

    • Author(s)
      Jheng Nai-Yuan、Ishizaka Yusuke、Naganawa Yuki、Sekiguchi Akira、Nakajima Yumiko
    • Journal Title

      Dalton Transactions

      Volume: 49 Issue: 41 Pages: 14592-14597

    • DOI

      10.1039/d0dt02549f

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Decarboxylation of Silyl Alkynoates to Alkynylsilanes2020

    • Author(s)
      Kawatsu Takahiro、Aoyagi Keiya、Nakajima Yumiko、Choi Jun-Chul、Sato Kazuhiko、Matsumoto Kazuhiro
    • Journal Title

      Organometallics

      Volume: 39 Issue: 16 Pages: 2947-2950

    • DOI

      10.1021/acs.organomet.0c00433

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Polypropylene-Based Nanocomposite with Enhanced Aging Stability by Surface Grafting of Silica Nanofillers with a Silane Coupling Agent Containing an Antioxidant2020

    • Author(s)
      Watanabe Ryota、Sugahara Aki、Hagihara Hideaki、Sakamoto Kei、Nakajima Yumiko、Naganawa Yuki
    • Journal Title

      ACS Omega

      Volume: 5 Issue: 21 Pages: 12431-12439

    • DOI

      10.1021/acsomega.0c01198

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Oxidative Addition of C?X Bonds and H?H Activation Using PNNP‐Iron Complexes2020

    • Author(s)
      Gautam Monika、Yatabe Takafumi、Tanaka Shinji、Satou Naoto、Takeshita Tomohiro、Yamaguchi Kazuya、Nakajima Yumiko
    • Journal Title

      ChemistrySelect

      Volume: 5 Issue: 1 Pages: 15-17

    • DOI

      10.1002/slct.201904616

    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Nickel-Catalyzed Selective Cross-Coupling of Chlorosilanes with Organoaluminum Reagents2019

    • Author(s)
      Naganawa Yuki、Guo Haiqing、Sakamoto Kei、Nakajima Yumiko
    • Journal Title

      ChemCatChem

      Volume: 印刷中 Issue: 16 Pages: 3756-3759

    • DOI

      10.1002/cctc.201900047

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of hydrosilanes via Lewis-base-catalysed reduction of alkoxy silanes with NaBH42019

    • Author(s)
      Aoyagi Keiya、Ohmori Yu、Inomata Koya、Matsumoto Kazuhiro、Shimada Shigeru、Sato Kazuhiko、Nakajima Yumiko
    • Journal Title

      Chemical Communications

      Volume: 印刷中 Issue: 42 Pages: 5859-5862

    • DOI

      10.1039/c9cc01961h

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Heterogeneous hydrosilylation reaction catalysed by platinum complexes immobilized on bipyridine-periodic mesoporous organosilicas2019

    • Author(s)
      Naganawa Yuki、Maegawa Yoshifumi、Guo Haiqing、Gholap Sandeep Suryabhan、Tanaka Shinji、Sato Kazuhiko、Inagaki Shinji、Nakajima Yumiko
    • Journal Title

      Dalton Transactions

      Volume: 48 Issue: 17 Pages: 5534-5540

    • DOI

      10.1039/c9dt00078j

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis and Characterization of Silyl-Bridged Dinuclear Cobalt Complexes Supported by an N-Heterocyclic Carbene2019

    • Author(s)
      Ishizaka Yusuke、Nakajima Yumiko
    • Journal Title

      Organometallics

      Volume: 38 Issue: 4 Pages: 888-893

    • DOI

      10.1021/acs.organomet.8b00865

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Deprotonation of a PNNP-Iron Complex: Expanding the Concept of Metal-ligand Cooperation to the PNNP-Iron System2019

    • Author(s)
      Takeshita Tomohiro、Nakajima Yumiko
    • Journal Title

      Chemistry Letters

      Volume: 48 Issue: 4 Pages: 364-366

    • DOI

      10.1246/cl.181027

    • NAID

      130007624444

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Reduction of Alkoxysilanes with Borane Using a Metallocene-Type Yttrium Complex2018

    • Author(s)
      Aoyagi Keiya、Matsumoto Kazuhiro、Shimada Shigeru、Sato Kazuhiko、Nakajima Yumiko
    • Journal Title

      Organometallics

      Volume: 38 Issue: 2 Pages: 210-212

    • DOI

      10.1021/acs.organomet.8b00798

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Selective hydrosiloxane synthesis via dehydrogenative coupling of silanols with hydrosilanes catalysed by Fe complexes bearing a tetradentate PNNP ligand2018

    • Author(s)
      Takeshita Tomohiro、Sato Kazuhiko、Nakajima Yumiko
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 47 Pages: 17004-17010

    • DOI

      10.1039/c8dt04168g

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Direct Silyl?Heck Reaction of Chlorosilanes2018

    • Author(s)
      Matsumoto Kazuhiro、Huang Jiadi、Naganawa Yuki、Guo Haiqing、Beppu Teruo、Sato Kazuhiko、Shimada Shigeru、Nakajima Yumiko
    • Journal Title

      Organic Letters

      Volume: 20 Issue: 8 Pages: 2481-2484

    • DOI

      10.1021/acs.orglett.8b00847

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-Pot Sequence-Controlled Synthesis of Oligosiloxanes2018

    • Author(s)
      Matsumoto Kazuhiro、Oba Yuki、Nakajima Yumiko、Shimada Shigeru、Sato Kazuhiko
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 57 Issue: 17 Pages: 4637-4641

    • DOI

      10.1002/anie.201801031

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hydrosilane synthesis via catalytic hydrogenolysis of halosilanes using a metal-ligand bifunctional iridium catalyst2018

    • Author(s)
      Beppu Teruo、Sakamoto Kei、Nakajima Yumiko、Matsumoto Kazuhiro、Sato Kazuhiko、Shimada Shigeru
    • Journal Title

      Journal of Organometallic Chemistry

      Volume: 869 Pages: 75-80

    • DOI

      10.1016/j.jorganchem.2018.05.024

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Presentation] パラジウム/カルボン酸触媒を用いるフルフラール類のアルキンによるアルケニル化反応2021

    • Author(s)
      南安規、宮本仁美、中島裕美子
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] オリゴシロキサンで連結された金属-ケイ素二重結合をもつ二核錯体:合成および1Dチャネル結晶構造2021

    • Author(s)
      中村 亮、松本 和弘、長田 浩一、河津 貴大、中島 裕美子、橋本 久子
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] シリルアルキノエートの触媒的脱炭酸を用いたアルキニルシランの合成2021

    • Author(s)
      河津 貴大、青柳 圭哉、片岡 祥、中島 裕美子、深谷 訓久、崔 準哲、佐藤 一彦、松本 和弘
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] PNNP-コバルト錯体による 金属-配位子協働効果2021

    • Author(s)
      中島裕美子、佐藤一彦
    • Organizer
      創造機能化学第116委員会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] Catalytic Hydrodehalogenation of Aryl Halides Mediated by a Long-Range Metal-Ligand Cooperation of Cobalt(I) Complexes Bearing a Tetradentate PNNP Ligand2021

    • Author(s)
      Nai-Yuan Jehng、永縄友規、中島裕美子
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 固体DNP-NMRを活用するポリマー担持型有機触媒の開発2021

    • Author(s)
      田中真司、中島裕美子、佐藤一彦
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] パラジウム触媒を用いるジ、トリ、テトラクロロシランからのメチルモノクロロシランへの選択的変換反応2021

    • Author(s)
      永縄友規、坂本圭、中島裕美子
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Hydrosilylation of Functionalized Alkenes2021

    • Author(s)
      Yumiko Nakajima* and Yuki Naganawa, Koya Inomata, Kei Sakamoto, Kazuhiko Sato
    • Organizer
      CCE-2021
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] A Well-Defined Fe Catalyst System Bearing a Tetradentate PNNP Ligand: Selective Synthesis of Hydrosiloxanes via Dehydronegative Coupling of Silanols with Hydrosilanes2019

    • Author(s)
      中島 裕美子、竹下智博、佐藤 一彦
    • Organizer
      4th Edition of International Conference on Catalysis and Green Chemistry
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Transition Metal-Catalyzed Precise Synthesis of Organosilicon Compounds Starting from Halosilanes2019

    • Author(s)
      中島 裕美子、永縄 友規、松本 和弘、別部輝生、佐藤 一彦、島田 茂
    • Organizer
      The 7th Asian Silicon Symposium,singapore
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 有機ケイ素化合物の精密合成を指向した触媒反応開発2019

    • Author(s)
      中島裕美子
    • Organizer
      第8回多元研男女参画推進セミナー
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] 精密有機ケイ素化合物合成の最前線2019

    • Author(s)
      中島裕美子
    • Organizer
      触媒学会ファインケミカルズ合成触媒研究会セミナー
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Nickel-Catalyzed Selective Cross-Coupling of Chlorosilanes with Organoaluminum Reagents2019

    • Author(s)
      永縄 友規、郭 海卿、坂本 圭、中島 裕美子
    • Organizer
      The 7th Asian Silicon Symposium,singapore
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] ニッケル触媒を用いるクロロシランの高効率触媒的分子変換2019

    • Author(s)
      永縄 友規、佐藤 一彦、中島 裕美子
    • Organizer
      第8回JACI/GSCシンポジウム
    • Related Report
      2019 Annual Research Report
  • [Presentation] ニッケル触媒を用いるクロロシランの高効率触媒的分子変換2018

    • Author(s)
      永縄 友規、佐藤 一彦、中島 裕美子
    • Organizer
      第8回JACI/GSCシンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] Si-Cl結合の酸化的付加反応を鍵とするクロロ(シリル)鉄錯体の合成と性質2018

    • Author(s)
      竹下 智博、中島 裕美子
    • Organizer
      第22回ケイ素化学協会シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] クロロシラン類の酸化的付加を鍵とする触媒的分子変換2018

    • Author(s)
      永縄 友規、別部輝生、松本 和弘、郭 海卿、佐藤 一彦、中島 裕美子
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Ni/Cu触媒によるクロロシラン類の選択的モノアルキニル化反応2018

    • Author(s)
      別部 輝生、松本 和弘、佐藤 一彦、中島 裕美子
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Catalytic Transformation of Chlorosilanes with Nickel Catalysts2018

    • Author(s)
      永縄 友規、別部輝生、松本 和弘、黄佳テイ、郭 海卿、佐藤 一彦、島田 茂、中島 裕美子
    • Organizer
      9th European Silicon Days
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Selective Synthesis of Hydrosiloxanes via Dehydronegative Coupling of Silanols with Hydrosilanes Catalyzed by Iron complexes Bearing a PNNP ligand2018

    • Author(s)
      竹下 智博、佐藤 一彦、中島 裕美子
    • Organizer
      International Conference on Coordination Chemistry (ICCC)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Facile Si-Cl Bond Cleavage Induced by a PNNP-supported Fe(0) Complex2018

    • Author(s)
      竹下 智博、中島 裕美子
    • Organizer
      ISCHA-4
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] クロロシラン類の酸化的付加を利用する触媒的分子変換2018

    • Author(s)
      永縄 友規、中島 裕美子、佐藤 一彦
    • Organizer
      創造機能化学第116委員会合同分科会
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Si-Cl 結合切断を基軸とするクロロシラン類の触媒的分子変換反応の開発2018

    • Author(s)
      中島裕美子
    • Organizer
      理研シンポジウム 第19回分析・解析技術と化学の最先端
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Catalytic Transformation of Chlorosilanes to Useful Organoesilicon Compounds2018

    • Author(s)
      中島裕美子
    • Organizer
      BIT’s 4th Annual World Congress of Smart Materials-2018 (WCSM-2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited

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Published: 2018-04-23   Modified: 2022-01-27  

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