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Asymmetric Molecular Transformation of Glycerines Based on Activation of Hydroxyl Groups

Research Project

Project/Area Number 19K05459
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionNagasaki University

Principal Investigator

ONOMURA OSAMU  長崎大学, 医歯薬学総合研究科(薬学系), 教授 (60304961)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2021: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2020: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2019: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywords不斉酸化 / グリセリン / 水酸基活性化 / グリセリン酸 / 不斉非対称化 / グリセロリン酸 / 不斉合成素子 / 不斉スルホニル化 / キラル合成素子
Outline of Research at the Start

グリセリンの余剰問題を解決するために、グリセリンの有効利用法開発が求められている。本課題では、グリセリンを医薬品等の原料となる光学活性化合物への変換法を開発する。具体的には、グリセリンから医薬品や液晶の重要な原料である光学活性グリシジルスルホネートへの変換法、グリセリン酸への酸化法、レシチンやセラミド機能物質への変換法の確立を目指している。ごく少量の触媒を用いてそれら変換反応を達成できる、不斉触媒の開発を行う。

Outline of Final Research Achievements

Lewis acids coordinate with diols to activate one hydroxyl group of diols, and then easily afford the successive reaction. Using chiral Lewis acids afforded the corresponded chiral compounds.
After the optimization of ligand-structures was accomplished, the oxidation under the improved reaction condition proceeded to afford various 2-subtituted glyceric esters in high yields and enantioselectivities.

Academic Significance and Societal Importance of the Research Achievements

本研究により、グリセリンから医薬品や液晶の重要な原料となる光学活性グリシジルスルホネートへの変換法、グリセリン酸への酸化法、グリセロリン酸を始めとするレシチンやセラミド機能物質への変換法を見出すことができた。本成果は、バイオディーゼルの普及に伴い派生したグリセリンの余剰問題の解決法となり得る。グリセリンや2位置換グリセリンをごく少量の触媒を用いて不斉変換できれば価値が高いが、その3つの水酸基を不斉識別して反応させることは大変難しかったが、本研究により高効率に達成できた。

Report

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

    (34 results)

All 2022 2021 2020 2019 Other

All Journal Article (15 results) (of which Peer Reviewed: 15 results,  Open Access: 1 results) Presentation (13 results) (of which Int'l Joint Research: 7 results,  Invited: 2 results) Book (1 results) Remarks (1 results) Patent(Industrial Property Rights) (4 results)

  • [Journal Article] Copper-Catalyzed Asymmetric Oxidative Desymmetrization of 2-Substituted 1,2,3-Triols2022

    • Author(s)
      Yamamoto Kosuke、Suganomata Yu、Inoue Takumi、Kuriyama Masami、Demizu Yosuke、Onomura Osamu
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 87 Issue: 9 Pages: 6479-6491

    • DOI

      10.1021/acs.joc.2c00398

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 12 Asymmetric Electrosynthesis2022

    • Author(s)
      Yamamoto K.、Kuriyama M.、Onomura O.
    • Journal Title

      Science of Synthesis: Electrochemistry in Organic Synthesis

      Volume: 1 Pages: 363-386

    • DOI

      10.1055/sos-sd-236-00237

    • ISBN
      9783132442122, 9783132442146
    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [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] Electrophotochemical Ring-Opening Bromination of tert-Cycloalkanols2021

    • Author(s)
      Yamamoto Kosuke、Toguchi Hiroyuki、Kuriyama Masami、Watanabe Shin、Iwasaki Fumiaki、Onomura Osamu
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 86 Issue: 22 Pages: 16177-16186

    • DOI

      10.1021/acs.joc.1c01264

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric electrosynthesis: Recent advances in catalytic transformations2021

    • Author(s)
      Yamamoto Kosuke、Kuriyama Masami、Onomura Osamu
    • Journal Title

      Current Opinion in Electrochemistry

      Volume: 28 Pages: 100714-100714

    • DOI

      10.1016/j.coelec.2021.100714

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Shono‐type Oxidation for Functionalization of N‐Heterocycles2021

    • Author(s)
      Yamamoto Kosuke、Kuriyama Masami、Onomura Osamu
    • Journal Title

      The Chemical Record

      Volume: 21 Issue: 9 Pages: 2239-2253

    • DOI

      10.1002/tcr.202100031

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Transition Metal-Free O-Arylation of Quinoxalin-2-ones with Diaryliodonium Salts2021

    • Author(s)
      Kuriyama Msami、Mochizuki Yuki、Miyagi, Tsubasa、Yamamoto Kosuke、Demizu Yosuke、Onomura Osamu
    • Journal Title

      Heterocycles

      Volume: 103 Issue: 1 Pages: 502-502

    • DOI

      10.3987/com-20-s(k)26

    • Related Report
      2020 Research-status 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] Anodic Oxidation for the Stereoselective Synthesis of Heterocycles2020

    • Author(s)
      Yamamoto Kosuke、Kuriyama Masami、Onomura Osamu
    • Journal Title

      Accounts of Chemical Research

      Volume: 53 Issue: 1 Pages: 105-120

    • DOI

      10.1021/acs.accounts.9b00513

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Copper‐Catalyzed Enantioselective Synthesis of Oxazolines from Aminotriols via Asymmetric Desymmetrization2020

    • Author(s)
      Yamamoto Kosuke、Tsuda Yutaro、Kuriyama Masami、Demizu Yosuke、Onomura Osamu
    • Journal Title

      Chemistry An Asian Journal

      Volume: 15 Issue: 6 Pages: 840-846

    • DOI

      10.1002/asia.201901742

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Oxidative C-C Bond Cleavage of N-Protected Cyclic Amines by HNO3-TFA System2020

    • Author(s)
      Onomura Osamu、Yamamoto Kosuke、Toguchi Hiroyuki、Harada Toshihiro、Kuriyama Masami
    • Journal Title

      HETEROCYCLES

      Volume: 101 Issue: 2 Pages: 486-495

    • DOI

      10.3987/com-19-s(f)31

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [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] Facile Synthesis of α-exo-Methylene Ketones from α,α-Disubstituted Allyl Alcohols  by Electrochemical Oxidative Migration2019

    • Author(s)
      Yamamoto, K.; Kikuchi, N.; Hamamizu, T.; Yoshimatsu, H.; Kuriyama, M.; Demizu, Y.; Onomura, O.
    • Journal Title

      ChemElectroChem

      Volume: 印刷中 Issue: 16 Pages: 4169-4172

    • DOI

      10.1002/celc.201900172

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Diastereodivergent Synthesis of Bromoiminolactones: Electrochemical and Chemical Bromoiminolactonization of α-Allylmalonamides2019

    • Author(s)
      Yamamoto Kosuke、Ishimaru Keiko、Mizuta Satoshi、Minato Daishirou、Kuriyama Masami、Onomura Osamu
    • Journal Title

      Synlett

      Volume: 印刷中 Issue: 10 Pages: 1204-1208

    • DOI

      10.1055/s-0037-1611791

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Synthesis of α-Substituted Serine Derivatives via Cu-Catalyzed  Oxidative Desymmetrization of 2-Amino-1,3-diols2019

    • Author(s)
      Yamamoto, K.; Ishimaru, S.; Oyama, T.; Tanigawa, S.; Kuriyama, M.; Onomura, O.
    • Journal Title

      Org. Process Res. Dev.

      Volume: 23 Issue: 4 Pages: 660-666

    • DOI

      10.1021/acs.oprd.8b00407

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] キラルビスオキサゾリン配位子を用いたトリオール類の銅触媒的不斉酸化2022

    • Author(s)
      井上拓海、菅野又裕、山本耕介、栗山正巳、尾野村治
    • Organizer
      日本薬学会第142年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] キラル銅触媒を用いたトリオール類の酸化的不斉非対称化2021

    • Author(s)
      井上拓海、菅野又裕、山本耕介、栗山正巳、尾野村治
    • Organizer
      第58回化学関連支部合同九州大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Copper ion-catalyzed asymmetric desymmetrization of prochiral 1,3-diols2021

    • Author(s)
      Onomura Osamu
    • Organizer
      Pacifichem 2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of Oxazoles via Rhodium-Catalyzed Denitrogenative Trans formation of Triazoles with Esters2021

    • Author(s)
      Yuya Kaieda, Kosuke yamamoto, Masami Kuriyama, Osamu Onomura
    • Organizer
      AIMECS2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 銅触媒を用いたグリセリン類の不斉酸化反応2021

    • Author(s)
      井上拓海、菅野又裕、山本耕介、栗山正巳、尾野村治
    • Organizer
      日本薬学会第141年会
    • Related Report
      2020 Research-status Report
  • [Presentation] Anodic Oxidation for the Stereoselective Synthesis of heterocycles2020

    • Author(s)
      Osamu Onomura
    • Organizer
      ISOR-14
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Nickel-catalyzed cross-coupling of bromodifluoromethylphosphnic acid diethyl ester and aryl boroxines2020

    • Author(s)
      Genki Maeda, Yusuke Kodama, Masami Kuriyama, Kosuke Yamamoto, Osamu Onomura
    • Organizer
      ISOR-14
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Presentation] 不斉四級炭素を有する光学活性アジリジンを活用したキラルビルディングブロックの合成2019

    • Author(s)
      上原杏梨、山本耕介、坂田英武、栗山正巳、尾野村治
    • Organizer
      日本薬学会九州支部大会
    • Related Report
      2019 Research-status Report
  • [Presentation] 不斉四級炭素を有する光学活性アジリジンを用いたキラル合成素子の創製2019

    • Author(s)
      上原杏梨、山本耕介、坂田英武、栗山正巳、尾野村治
    • Organizer
      反応と合成の進歩シンポジウム
    • Related Report
      2019 Research-status Report
  • [Presentation] アンモニウム塩によるハロイミノラクトン化のジアステレオ選択性制御2019

    • Author(s)
      尾野村治、菊池直登、石丸景子、山本耕介、栗山正巳
    • Organizer
      電気化学会秋季大会
    • Related Report
      2019 Research-status Report
  • [Presentation] Regioselective Addition of Quinoline Derivatives to Carbonyl Compounds via Pd-catalyzed Umplung with Diethyl Zinc2019

    • Author(s)
      Yohei Matsumoto, Kosuke Yamamoto, Masami Kuriyama, Osamu Onomura
    • Organizer
      27th Intenational Society of Heterocyclic Chemistry Congress
    • 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)
      Yusuke Abe, Natsumi Hanazawa, Shinpei Ono, Masami Kuriyama, Kosuke Yamamoto, Osamu Oのむら
    • Organizer
      The 4th International Symposium on Process Chemistry [ISPC 2019]
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Nucleophilic C2-arylation of quinolines using diarliodoniumu salts2019

    • Author(s)
      Tatsuya Sugiyama, Kosuke Yamamoto, Masami Kuriyama, Osamu Onomura
    • Organizer
      The 4th International Symposium on Process Chemistry [ISPC 2019]
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Book] 有機電解合成 ―環境調和型プロセスと特異な反応場の構築を目指して―2021

    • Author(s)
      山本耕介、栗山正巳、尾野村 治
    • Total Pages
      13
    • Publisher
      (株)シーエムシー出版
    • Related Report
      2021 Annual Research Report
  • [Remarks] 長崎大学薬学部医薬品合成化学分野

    • URL

      http://www.ph.nagasaki-u.ac.jp/lab/synchem/index-j.html

    • Related Report
      2021 Annual Research Report 2020 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、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、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)] 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、楠本悠紀他
    • Industrial Property Rights Holder
      尾野村治、栗山正巳、山本耕介、菊池直登、上原杏梨、楠本悠紀他
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2019-109306
    • Filing Date
      2019
    • Related Report
      2019 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
      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 Type
      特許
    • Industrial Property Number
      2019-110229
    • Filing Date
      2019
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2023-01-30  

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