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Synthesis of All Diastereomers of Vicinal Diamines from Alkenes

Research Project

Project/Area Number 19H02716
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 InstitutionOsaka University

Principal Investigator

Minakata Satoshi  大阪大学, 工学研究科, 教授 (90273599)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥17,550,000 (Direct Cost: ¥13,500,000、Indirect Cost: ¥4,050,000)
Fiscal Year 2021: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2020: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2019: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000)
Keywordsジアミノ化 / 立体特異的反応 / アルケン / ジアミン / アンチ付加 / シン付加
Outline of Research at the Start

本研究では、実践的な方法論が未だ確立されていないアルケンのビシナルジアミノ化を取り上げ、不斉合成も含めたアンチ付加とシン付加の完全な立体制御に取り組む。本提案は、活性三員環を経由する完全アンチ付加と、二つの反応部位を分子内に有する窒素原を用いる完全シン付加を可能にする。単純な反応であるがゆえに、既に知られた反応のように思われるが、実際には存在せず、教科書に取り上げられても不思議ではない程の学術的に意義深い方法論となるだけでなく、これまでこのタイプの実践的な反応が存在しなかったが故に、複雑な医薬品や機能性物質の合成が短工程となり、価値ある反応開拓である

Outline of Final Research Achievements

The 1,2-diamine motif is a ubiquitous feature of bioactive compounds and ligands for organic synthesis, and valuable synthetic intermediates for constructing complex molecules. Although controlling the relative configuration of two nitrogen moieties is crucial for the synthesis of diverse molecules, there are no versatile methods available the enable the anti- and syn-diamination of alkenes with complete control of the stereochemistry. In this research we realized the stereospecific, substrate-controlled intermolecular anti- and syn-1,2-diamination of a broad range of unactivated alkenes using the same catalysis. The concomitant use of the two methods provides access to all of the disastereomeric forms of 1,2-diamines in spite of the availability of E- and Z-alkenes, and the resulting products can be converted into free vicinal diamines. The diamination reactions are green sustainable because the waste by-products that are produced in the reactions are only NaCl and/or H2O.

Academic Significance and Societal Importance of the Research Achievements

有機合成反応の開拓は、川上に位置する研究ではあるが、今回見出した立体制御が可能なジアミノ化反応は、一般性および汎用性が高く、新薬の合成に十分貢献できるものである。新型コロナウイルスの発現とその感染拡大で、世界中がその恐怖にさらされている。ワクチンの開発が急速に進んでいるが、抗ウイルス薬の開拓も急務な課題であることは言うまでもない。一部の抗インフルエンザ薬の中に1,2-ジアミン骨格が含まれるからといって、新型コロナウイルスの特効薬に使える保証は全くないが、これまでになかった反応は、新しい物質を迅速に合成することを可能にし、例えば新薬の候補化合物群の合成を加速することが期待できる。

Report

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

    (20 results)

All 2022 2021 2020 2019

All Journal Article (9 results) (of which Peer Reviewed: 9 results) Presentation (11 results) (of which Invited: 2 results)

  • [Journal Article] A practical method for the aziridination of α,β-unsaturated carbonyl compounds with a simple carbamate utilizing sodium hypochlorite pentahydrate2021

    • Author(s)
      Umeda Takehiro、Minakata Satoshi
    • Journal Title

      RSC Advances

      Volume: 11 Issue: 36 Pages: 22120-22124

    • DOI

      10.1039/d1ra04297a

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Fused Diaziridine Derivatives from Cyclic Secondary Amines by Utilizing N-Bromosulfonamides as an Aminating Reagent2021

    • Author(s)
      Minakata Satoshi、Kiyosu Yuuki、Tanaka Shino、Okumura Sota、Kiyokawa Kensuke
    • Journal Title

      Synthesis

      Volume: 53 Issue: 17 Pages: 3101-3109

    • DOI

      10.1055/a-1468-8275

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Diastereodivergent Intermolecular 1,2-Diamination of Unactivated Alkenes Enabled by Iodine Catalysis2021

    • Author(s)
      Minakata Satoshi、Miwa Hayato、Yamamoto Kenya、Hirayama Arata、Okumura Sota
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 11 Pages: 4112-4118

    • DOI

      10.1021/jacs.1c00228

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Transition-Metal-Free Aziridination of Alkenes with Sulfamate Esters Using tert-Butyl Hypoiodite2021

    • Author(s)
      Minakata Satoshi、Kiyokawa Kensuke、Nakamura Shogo
    • Journal Title

      HETEROCYCLES

      Volume: 103 Issue: 1 Pages: 190-190

    • DOI

      10.3987/com-20-s(k)20

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Iodine-Based Reagents in Oxidative Amination and Oxygenation2020

    • Author(s)
      Kiyokawa Kensuke、Minakata Satoshi
    • Journal Title

      Synlett

      Volume: 31 Issue: 09 Pages: 845-855

    • DOI

      10.1055/s-0039-1690827

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Hypervalent Iodine(III) Reagents Containing a Transferable (Diarylmethylene)amino Group and Their Use in the Oxidative Amination of Silyl Ketene Acetals2019

    • Author(s)
      Kensuke Kiyokawa, Daichi Okumatsu, and Satoshi Minakata
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 58 Issue: 26 Pages: 8907-8911

    • DOI

      10.1002/anie.201904971

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Synthesis of β 2‐Aryl Amino Acids through Pd‐Catalyzed Enantiospecific and Regioselective Ring‐Opening Suzuki-Miyaura Arylation of Aziridine‐2‐carboxylates2019

    • Author(s)
      Takeda Youhei、Matsuno Tetsuya、Sharma Akhilesh K.、Sameera W. M. C.、Minakata Satoshi
    • Journal Title

      Chemistry: A European Journal

      Volume: 25 Issue: 43 Pages: 10226-10231

    • DOI

      10.1002/chem.201902009

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalyst-Controlled Regiodivergent Ring-Opening C(sp3)-Si Bond-Forming Reactions of 2-Arylaziridines with Silylborane Enabled by Synergistic Palladium/Copper Dual Catalysis2019

    • Author(s)
      Youhei Takeda, Kaoru Shibuta, Shohei Aoki, Norimitsu Tohnai, and Satoshi Minakata
    • Journal Title

      Chem. Sci.

      Volume: 10 Issue: 37 Pages: 8642-8647

    • DOI

      10.1039/c9sc02507c

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Transition-Metal-Free Intramolecular C-H Amination of Sulfamate Esters and N-Alkylsulfamides2019

    • Author(s)
      Kensuke Kiyokawa, Shogo Nakamura, Keisuke Jou, Kohji Iwaida, and Satoshi Minakata
    • Journal Title

      Chem. Commun.

      Volume: 55 Issue: 78 Pages: 11782-11785

    • DOI

      10.1039/c9cc06410a

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Presentation] 単純なスルホンアミドを窒素源とする電子不足オレフィンのビシナルジアミノ化2022

    • Author(s)
      杉山 孟, 山田裕貴, 南方聖司
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] syn-Diamination of olefins with N,N’-bis(tert-butoxycarbonyl)sulfamide as a nitrogen source2021

    • Author(s)
      Ryosuke Mimata, Hayato Miwa, Kenya Yamamoto, Satoshi Minakata
    • Organizer
      2021 International Chemical Congress of Pacific Basin Societies
    • Related Report
      2021 Annual Research Report
  • [Presentation] Molecular iodine-catalyzed anti-1,2-diamination of olefins with nosylamide using sodium hypochlorite pentahydrate2021

    • Author(s)
      Yuki Yamada, Hayato Miwa, Arata Hirayama, Satoshi Minakata
    • Organizer
      2021 International Chemical Congress of Pacific Basin Societies
    • Related Report
      2021 Annual Research Report
  • [Presentation] N-ハロスルホンアミドを活用した電子不足オレフィンのビシナルジアミノ化2021

    • Author(s)
      山田裕貴, 柿崎優花, 清川謙介, 南方聖司
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] N,N-ジクロロ-2-ニトロベンゼンスルホンアミドを活用したエーテルのα位アミノ化2021

    • Author(s)
      三又亮介, 南方聖司
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] N,N-ジクロロトシルアミドを活用したベンジル位C-Hクロロ化2021

    • Author(s)
      水上 学, 南方聖司
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] N-ブロモスルホンアミドを活用する電子不足オレフィンの窒素官能基化2020

    • Author(s)
      柿崎優花, 南方聖司
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ハロゲン元素を操ってN1ユニットを導入する有機合成2019

    • Author(s)
      南方聖司
    • Organizer
      (公財)科学技術交流財団 第4回環境に優しいファインケミカル合成研究会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] ヨウ素酸化剤を活用したスルファマートエステルの分子内C-Hアミノ化2019

    • Author(s)
      中村彰悟, 清川謙介, 南方聖司
    • Organizer
      第22回ヨウ素学会シンポジウム
    • Related Report
      2019 Annual Research Report
  • [Presentation] ヨウ素を活用する有機合成反応2019

    • Author(s)
      南方聖司
    • Organizer
      第36回有機合成化学セミナー
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] ヨウ素触媒によるアルケンとN-クロロアミドからのオキサゾリン合成2019

    • Author(s)
      柿崎優花, 南方聖司
    • Organizer
      第9回CSJ化学フェスタ2019
    • Related Report
      2019 Annual Research Report

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

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