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Asymmetric Amination Catalyzed by Dirhodium(II) Complexes

Research Project

Project/Area Number 19790001
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionHokkaido University

Principal Investigator

ANADA Masahiro  Hokkaido University, 大学院・薬学研究院, 助教 (90344473)

Project Period (FY) 2007 – 2008
Project Status Completed (Fiscal Year 2008)
Budget Amount *help
¥3,690,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2008: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2007: ¥2,000,000 (Direct Cost: ¥2,000,000)
Keywords合成化学 / 不斉触媒反応 / ロジウム(II)錯体 / イミノヨーディナン / ナイトレン / α-アミノケトン / ベンゾモルファン化合物 / α-フェニルグリシン誘導体 / アジリジン
Research Abstract

ロジウム(II) 錯体触媒を用いた、スルホニルイミノヨージナンをナイトレン前駆体とする鎖状ケトン由来のシリルエノールエーテルの不斉アミノ化反応ついて検討を行った。その結果、NsN=IPh (Ns = 2-NO2C6H4SO2)をナイトレン前駆体、Rh2(S-TFPTTL)4 を触媒に用いると最高95%の不斉収率でα-アミノケトンが得られることを見出し、本法を機軸とする(.)-リトドリン、(.)-メタゾシンの触媒的不斉合成を達成した。また、ベンゼン溶媒中Rh2(S-TCPTTL)4を触媒に用いフェニル酢酸由来のシリルケテンアセタールの不斉アミノ化反応を行うとフェニルグリシン誘導体が最高不斉収率99%で得られることが判明した。さらに、シクロヘキサノン由来のシリルエノールエーテルを基質とした場合にはアリル位C.H結合へのナイトレンの挿入反応が位置およびエナンチオ選択的に進行することを見出し、本法を鍵工程とするヒガンバナアルカロイド(.)-パンクラシンの形式不斉合成を達成した。

Report

(3 results)
  • 2008 Annual Research Report   Final Research Report ( PDF )
  • 2007 Annual Research Report
  • Research Products

    (28 results)

All 2009 2008 2007 Other

All Journal Article (16 results) (of which Peer Reviewed: 16 results) Presentation (9 results) Patent(Industrial Property Rights) (3 results)

  • [Journal Article] Asymmetric Formal Synthesis of (-)-Pancracine via Catalytic Enantioselective C-HAmination Process2009

    • Author(s)
      Anada, M, Tanaka, M, Shimada, N, Nambu, H, Yamawaki, M, Hashimoto, S
    • Journal Title

      Tetrahedron 65

      Pages: 3069-3077

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Formal Synthesis of (-)-Pancracine via Catalytic Enantioselective C-H Amination Process2009

    • Author(s)
      M. Anada et.al.
    • Journal Title

      Tetrahedron 65

      Pages: 3069-3077

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Asymmetric Synthesis of (-)-Ritodrine Hydrochloride via Silyl Enol Ether Amination Using Dirhodium(II) Tetrakis[tetrafluorophthaloyl-(S)-tert-leucinate]2008

    • Author(s)
      Tanaka, M, Nakamura, S, Anada, M, Hashimoto, S
    • Journal Title

      Heterocycles 76

      Pages: 1633-1645

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Enantioselective Intermolecular Cycloaddition of 2-Diazo-3,6-diketo -ester-Derived Carbonyl Ylides with Alkynes and Styrenes Using Chiral Dirhodium(II) Carboxylates2008

    • Author(s)
      Shimada, N, Anada, M, Nakamura, S, Nambu, H, Tsutsui, H, Hashimoto, S
    • Journal Title

      Org. Lett 10

      Pages: 3603-3606

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Enantioselective Intermolecular Cycloaddition of 2-Diazo-3, 6-diketoester-Derived Carbonyl Ylides with Alkynes and Styrenes Using Chiral Dirhodium(II) Carboxylates2008

    • Author(s)
      N. Shimada et.al.
    • Journal Title

      Organic Letters 10

      Pages: 3603-3606

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Asymmetric Synthesis of (-)-Ritodrine Hydrochloride via Silyl Enol Ether Amination Using Dirhodium(II) Tetrakis[tetrafluorophthaloy1-(S)-tert-leucinate]2008

    • Author(s)
      M. Tanaka et.al.
    • Journal Title

      Heterocycles 76

      Pages: 1633-1645

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Asymmetric Hetero-Diels-Alder Route to a Key Intermediate for the Synthesis of Calyxin L2007

    • Author(s)
      Washio, T, Nambu, H, Anada, M, Hashimoto, S
    • Journal Title

      Tetrahedron: Asymmetry 18

      Pages: 2606-2612

    • NAID

      120000950252

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Amination of Silylketene Acetals with (N-Arylsulfonylimino)phenyliodinanes Catalyzed by Chiral Dirhodium(II) Carboxylates: Asymmetric Synthesis of Phenylglycine Derivatives2007

    • Author(s)
      Tanaka, M, Kurosaki, Y, Washio, T, Anada, M, Hashimoto, S
    • Journal Title

      Tetrahedron Lett 48

      Pages: 8799-8802

    • NAID

      120000950257

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Enantioselective Amination of Silyl Enol Ethers Using Chiral Dirhodium(II) Carboxylates: Asymmetric Formal Synthesis of (-)-Metazocine2007

    • Author(s)
      Anada, M, Tanaka, M, Washio, T, Yamawaki, M, Abe, T, Hashimoto, S
    • Journal Title

      Org. Lett 9

      Pages: 4559-4562

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Syntheses of Diarylheptanoid Natural Products, (-)-Centrolobine and (-)-de-O-Methylcentrolobine via Hetero-Diels-Alder Reaction Catalyzed by Dirhodium(II) Tetrakis[(R)-3-(benzene -fused-phthalimido)-2-piperidinonate]2007

    • Author(s)
      Washio, T, Yamaguchi, R, Abe, T, Nambu, H, Anada, M, Hashimoto, S
    • Journal Title

      Tetrahedron 63

      Pages: 12037-12046

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Enantioselective Aziridination of Alkenes Using Chiral Dirhodium(II) Carboxylate2007

    • Author(s)
      Yamawaki, M, Tanaka, M, Abe, T, Anada, M, Hashimoto, S
    • Journal Title

      Heterocycles 72

      Pages: 709-721

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Enantioselective Tandem Carbonyl Ylide Formation/1,3-Dipolar Cycloaddition Reactions of α-Diazo Ketones with Aromatic Aldehydes Using Dirhodium(II) Tetrakis[N-benzene-fused-phthaloyl(S)-valinate]2007

    • Author(s)
      Tsutsui, H, Shimada, N, Abe, T, Anada, M, Nakajima, M, Nakamura, S, Nambu, H, Hashimoto, S
    • Journal Title

      Adv. Synth. Catal 349

      Pages: 521-526

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Enantioselective Aziridimation of Alkeness Using Chiral Dirhodium(II) Carboxylates2007

    • Author(s)
      M. Yamawaki et al.
    • Journal Title

      Heterocycles 72

      Pages: 709-721

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Enantioselective Amination of Silyl Enol Ethers Using Chiral Dirhodium(II) Carboxylates : Asymmetric Formal Synthesis of (-)-Metazocine2007

    • Author(s)
      M. Anada et al.
    • Journal Title

      Organic Letters 9

      Pages: 4559-4562

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Amination of Silylketene Acetals with (N-Arylsulfonylimino)Phenyliodimanes Catalyzed by Chiral Dirhodium(II) Carboxylates : Asymmetric Synthesis of Phenylglycine Derivatives2007

    • Author(s)
      M. Tanaka et al.
    • Journal Title

      Tetrahedron Letters 48

      Pages: 8799-8802

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Construction of 2,8-Dioxabicyclo[3.2.1]octane Ring System via [2,3]-Sigmatropic Rearrangement of Oxonium Ylide Using Chiral Dirhodium (II) Carboxylates

    • Author(s)
      Shimada, N., Nakamura, S., Anada, M., Shiro, M, Hashimoto, S
    • Journal Title

      Chem. Lett (in press)

    • NAID

      10025122221

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Presentation] A Dirhodium(II) Carboxamidate Complex as a Chiral Lewis Acid Catalyst for Enantioselective Hetero-Diels-Alder Reactions2008

    • Author(s)
      Anada, M, Washio, T, Watanabe, Y, Shimada, N, Hashimoto, S
    • Organizer
      3rd International Symposium on Cutting-Edge Organic Chemistry in Asia
    • Place of Presentation
      Hangzhou, China
    • Year and Date
      2008-10-20
    • Related Report
      2008 Final Research Report
  • [Presentation] Enantioselective Amination Reactions Catalyzed by Dirhodium(II) Carboxylates2008

    • Author(s)
      Tanaka, M, Kurosaki, Y, Washio, T, Anada, M, Hashimoto, S
    • Organizer
      17th International Conference on Organic Synthesis
    • Place of Presentation
      Daejeon, Korea
    • Year and Date
      2008-06-26
    • Related Report
      2008 Final Research Report
  • [Presentation] Dirhodium(II)-Catalyzed Enantioselective Hetero-Diels-Alder Reaction: Catalytic, Enantioselective Synthesis of Cyclic Diarylheptanoid Natural Products2008

    • Author(s)
      Washio, T, Anada, M, Hashimoto, S
    • Organizer
      17th International Conference on Organic Synthesis
    • Place of Presentation
      Daejeon, Korea
    • Year and Date
      2008-06-26
    • Related Report
      2008 Final Research Report
  • [Presentation] ロジウム(II)アミダート錯体触媒を用いた不斉ヘテロDiels-Alder 反応2008

    • Author(s)
      穴田仁洋
    • Organizer
      日本薬学会北海道支部第130回例会総説講演
    • Place of Presentation
      札幌
    • Year and Date
      2008-05-10
    • Related Report
      2008 Final Research Report
  • [Presentation] ロジウム(II)カルボキシラート錯体を用いる触媒的不斉アミノ化反2007

    • Author(s)
      穴田仁洋
    • Organizer
      若手研究者のための有機化学札幌セミナー
    • Place of Presentation
      札幌
    • Year and Date
      2007-10-05
    • Related Report
      2008 Final Research Report
  • [Presentation] Rh(II)-Catalyzed Enantioselective Hetero-Diels-Alder Reaction: Enantioselective Synthesis of Cyclic Diarylheptanoid Natural Products2007

    • Author(s)
      Washio, T, Anada, M, Hashimoto, S
    • Organizer
      14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS14)
    • Place of Presentation
      奈良
    • Year and Date
      2007-08-02
    • Related Report
      2008 Final Research Report
  • [Presentation] Dirhodium(II)-Catalyzed Enantioselective Hetero-Diels-Alder Reaction2007

    • Author(s)
      Anada, M, Washio, T, Watanabe, Y, Shimada, N, Hashimoto, S
    • Organizer
      第1回プロセス化学国際シンポジウム(ISPC08)
    • Place of Presentation
      京都
    • Year and Date
      2007-07-29
    • Related Report
      2008 Final Research Report
  • [Presentation] A Dirhodium(II) Carboxamidate Complex as a Chiral Lewis Acid Catalyst for Enantioselective Hetero-Diels-Alder Reaction" 特定領域研究「炭素資源の高度分子変換」2007

    • Author(s)
      Washio, T, Anada, M, Hashimoto. S
    • Organizer
      キラル有機分子触媒の国際シンポジウム
    • Place of Presentation
      大津
    • Year and Date
      2007-05-28
    • Related Report
      2008 Final Research Report
  • [Presentation] Enantioselective Aminations Catalyzed by Dirhodium(II) Carboxylates2007

    • Author(s)
      Anada, M, Tanaka, M, Yamawaki, M, Hashimoto, S
    • Organizer
      PSWC2007
    • Place of Presentation
      Amsterdam, Netherlands
    • Year and Date
      2007-04-23
    • Related Report
      2008 Final Research Report
  • [Patent(Industrial Property Rights)] 固相担持型金属錯体触媒2008

    • Inventor(s)
      橋本俊一, 穴田仁洋
    • Industrial Property Rights Holder
      北海道大学
    • Filing Date
      2008-01-31
    • Related Report
      2008 Final Research Report
  • [Patent(Industrial Property Rights)] α-アミノケトンの製法2007

    • Inventor(s)
      橋本俊一, 穴田仁洋
    • Industrial Property Rights Holder
      科学技術振興機構
    • Patent Publication Number
      2007-204442
    • Filing Date
      2007-08-16
    • Related Report
      2008 Final Research Report
  • [Patent(Industrial Property Rights)] 不斉触媒2007

    • Inventor(s)
      橋本俊一, 穴田仁洋
    • Industrial Property Rights Holder
      北海道大学
    • Patent Publication Number
      2007-203269
    • Filing Date
      2007-08-16
    • Related Report
      2008 Final Research Report

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Published: 2007-04-01   Modified: 2016-04-21  

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