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Development and application of the selective oxidation for alcohols by Pd catalysis

Research Project

Project/Area Number 18K06582
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 47010:Pharmaceutical chemistry and drug development sciences-related
Research InstitutionNagasaki University

Principal Investigator

Kuriyama Masami  長崎大学, 医歯薬学総合研究科(薬学系), 准教授 (40411087)

Project Period (FY) 2018-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2020: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywords触媒反応 / 酸化反応 / 化学選択性 / パラジウム / N-ヘテロ環状カルベン / アルコール / カルベン / 遷移金属
Outline of Final Research Achievements

The palladium-catalyzed selective oxidation of the heterocycle-containing alcohols was developed by using an N-heterocyclic carbene (NHC) ligand. In this research, the optimization of reaction conditions was conducted aimed at achieving the selective transformation of alcohols especially with reactive N-heterocycles. Our original catalyst system and the use of stable reoxidants allowed the alcohol oxidation for substrates bearing aromatic and aliphatic N-heterocycles with efficient selectivity. In this method, the challenging 1,2-aminoalcohols were also tolerated, and the high level of selectivity and the broad scope of substrates were realized.

Academic Significance and Societal Importance of the Research Achievements

類似した反応性をもつ官能基を区別して変換可能となれば保護・脱保護の工程が不要となり、医薬品をはじめとする有用分子の高効率合成が可能となる。これまでに報告されている選択的アルコール酸化手法は、1,2-アミノアルコール類などへの適用が難しく、合成的応用が限定された状態にあった。本研究では、これまで困難とされていた構造を含む幅広い対象に対して選択的アルコール酸化を効率的に実施可能とする新しい手法の開発に成功した。本手法の特徴を効果的に活用することにより、生物活性物質などの研究開発の加速と発展が期待される。

Report

(5 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Research-status Report
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (20 results)

All 2021 2020 2019 2018

All Journal Article (5 results) (of which Peer Reviewed: 5 results,  Open Access: 1 results) Presentation (11 results) (of which Int'l Joint Research: 3 results) Patent(Industrial Property Rights) (4 results)

  • [Journal Article] Nickel-Catalyzed Hydrodeoxygenation of Aryl Sulfamates with Alcohols as Mild Reducing Agents2021

    • Author(s)
      Kuriyama Masami、Onomura Osamu、Matsuo Kasumi、Yamamoto Kosuke、Demizu Yosuke、Nishida Koyo
    • Journal Title

      Synthesis

      Volume: 53 Issue: 23 Pages: 4449-4460

    • DOI

      10.1055/a-1548-8362

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] N- and O-arylation of pyridin-2-ones with diaryliodonium salts: base-dependent orthogonal selectivity under metal-free conditions2020

    • Author(s)
      Kuriyama, M.; Hanazawa, N.; Abe, Y.; Katagiri, K.; Ono, S.; Yamamoto, K.; Onomura, O.
    • Journal Title

      Chem. Sci.

      Volume: 11 Issue: 31 Pages: 8295-8300

    • DOI

      10.1039/d0sc02516j

    • NAID

      120006988537

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Palladium-catalyzed synthesis of deuterated alkenes through deuterodechlorination of alkenyl chlorides2019

    • Author(s)
      M. Kuriyama,* G. Yano, H. Kiba, T. Morimoto, K. Yamamoto, Y. Demizu, O. Onomura*
    • Journal Title

      Org. Process Res. Dev.

      Volume: 23 Issue: 8 Pages: 1552-1557

    • DOI

      10.1021/acs.oprd.9b00193

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] β-Trichloroacetylation of cyclic amines: application to synthesis of chiral azabicyclo-N-oxyls2019

    • Author(s)
      Kuriyama, M.; Kamogawa, S.; Yamamoto, K.; Onomura, O.
    • Journal Title

      Heterocycles

      Volume: 99 Issue: 2 Pages: 1020-1031

    • DOI

      10.3987/com-18-s(f)68

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Palladium-catalyzed chemoselective anaerobic oxidation of N-heterocycle-containing alcohols2018

    • Author(s)
      Kuriyama, M.; Nakashima, S.; Miyagi, T.; Sato, K.; Yamamoto, K.; Onomura, O.
    • Journal Title

      Org. Chem. Front.

      Volume: 5 Issue: 15 Pages: 2364-2369

    • DOI

      10.1039/c8qo00421h

    • NAID

      120006987984

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] ニッケル触媒による有機ホウ素試薬とジフルオロメチルホスホン酸類のカップリング反応2021

    • Author(s)
      前田源喜, 児玉祐昌, 栗山正巳, 山本耕介, 尾野村治
    • Organizer
      第38回日本薬学会九州山口支部大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 有機ヨードニウム塩を用いた 2-ピリドン類の選択性切替型アリール化反応2021

    • Author(s)
      栗山正巳, 花澤菜摘, 阿部裕介, 片桐琴音, 小野真平, 山本耕介, 尾野村治
    • Organizer
      第47回反応と合成の進歩シンポジウム
    • Related Report
      2021 Annual Research Report
  • [Presentation] アルコールを水素源に用いたNHC-Ni触媒による フェノール誘導体の還元的脱酸素化2021

    • Author(s)
      松尾佳澄, 栗山正巳, 山本耕介, 尾野村治
    • Organizer
      第10回JACI/GSCシンポジウム
    • Related Report
      2021 Annual Research Report
  • [Presentation] 非対称NHC-ニッケル触媒によるアリールスルファメートの水素化反応2020

    • Author(s)
      松尾佳澄, 栗山正巳, 山本耕介, 尾野村治
    • Organizer
      反応と合成の進歩2020特別企画シンポジウム
    • Related Report
      2020 Research-status Report
  • [Presentation] 有機ヨード二ウム塩を用いた2-キノキサリノンのO-選択的アリール化反応2020

    • Author(s)
      望月祐樹, 片桐琴音, 宮城翼, 栗山正巳, 山本耕介, 尾野村治
    • Organizer
      第49回複素環化学討論会
    • Related Report
      2020 Research-status Report
  • [Presentation] Nickel-catalyzed cross-coupling of bromodifluoromethylphosphonic acid diethyl ester and aryl boroxines2020

    • Author(s)
      Maeda, G.; Kodama, Y.; Kuriyama, M.; Yamamoto, K.; Onomura, O.
    • Organizer
      The 14th International Symposium on Organic Reactions, the 44th Symposium on Organic Electron Transfer Chemistry (EOC), and the 8th German Japanese (Global Joint) Symposium on Electrosynthesis
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Presentation] Palladium-catalyzed deoxygenative deuteration of aryl nonaflates2019

    • Author(s)
      Kuriyama, M.; Tsukuda, K.; Kiba, H.; Morimoto, T.; Yamamoto, K.; Onomura, O.
    • Organizer
      The 4th International Symposium on Process Chemistry
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Orthogonal selectivity controlled by organic bases in arylation for 2-pyridones with diaryliodonium salts2019

    • Author(s)
      Abe, Y.; Hanazawa, N.; Ono, S.; Kuriyama, M.; Yamamoto, K.; Onomura, O.
    • Organizer
      The 4th International Symposium on Process Chemistry
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] テトラヒドロイソキノリン類への酸化的ジフルオロ酢酸エステル導入2019

    • Author(s)
      木場広智,栗山正巳,山本耕介,尾野村治
    • Organizer
      第43回有機電子移動化学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] 非触媒的制御による2-ピリドン類の化学選択的アリール化反応2018

    • Author(s)
      栗山正巳,花澤菜摘,阿部裕介,小野真平,山本耕介,尾野村治
    • Organizer
      第48回複素環化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] ニッケル触媒を用いたブロモジフルオロメチルリン酸類と芳香族ボロキシンのカップリング反応2018

    • Author(s)
      児玉祐昌,栗山正巳,山本耕介,尾野村治
    • Organizer
      第44回反応と合成の進歩シンポジウム
    • Related Report
      2018 Research-status Report
  • [Patent(Industrial Property Rights)] ハロカルボニル化合物の製造方法2021

    • Inventor(s)
      尾野村治,栗山正巳,山本耕介,戸口裕之,渡辺伸,岩崎史哲
    • Industrial Property Rights Holder
      尾野村治,栗山正巳,山本耕介,戸口裕之,渡辺伸,岩崎史哲
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2021-040833
    • Filing Date
      2021
    • Related Report
      2020 Research-status Report
  • [Patent(Industrial Property Rights)] クロロメチル安息香酸エステル誘導体の製造方法2020

    • Inventor(s)
      尾野村治,栗山正巳,山本耕介,松浦圭介,林達,菊池直登
    • Industrial Property Rights Holder
      尾野村治,栗山正巳,山本耕介,松浦圭介,林達,菊池直登
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2020-203162
    • Filing Date
      2020
    • Related Report
      2020 Research-status Report
  • [Patent(Industrial Property Rights)] 塩素化ケトン化合物の製造方法2019

    • Inventor(s)
      尾野村治,栗山正巳,山本耕介,菊池直登,森脇正之,角田大
    • Industrial Property Rights Holder
      長崎大学,(株)トクヤマ
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2019-110229
    • Filing Date
      2019
    • Related Report
      2019 Research-status Report
  • [Patent(Industrial Property Rights)] カルボニル化合物の製造方法2019

    • Inventor(s)
      尾野村治,栗山正巳,山本耕介,菊池直登,上原杏梨,他3名
    • Industrial Property Rights Holder
      長崎大学,(株)トクヤマ
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2019-109306
    • Filing Date
      2019
    • Related Report
      2019 Research-status Report

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Published: 2018-04-23   Modified: 2023-01-30  

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