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多元素環状化合物の創製の研究総括

Research Project

Project/Area Number 12056101
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionThe University of Tokyo

Principal Investigator

奈良坂 紘一  東京大学, 大学院・理学系研究科, 教授 (50016151)

Co-Investigator(Kenkyū-buntansha) 橋本 俊一  北海道大学, 大学院・薬学系研究科, 教授 (80107391)
村上 正浩  京都大学, 大学院・工学研究科, 教授 (20174279)
岩澤 伸治  東京工業大学, 大学院・理工学研究科, 教授 (40168563)
伊藤 嘉彦  京都薬科大学, 薬学部, 教授 (40026018)
Project Period (FY) 2000 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥32,500,000 (Direct Cost: ¥32,500,000)
Fiscal Year 2004: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2003: ¥10,000,000 (Direct Cost: ¥10,000,000)
Fiscal Year 2002: ¥10,000,000 (Direct Cost: ¥10,000,000)
Fiscal Year 2001: ¥9,500,000 (Direct Cost: ¥9,500,000)
Keywords多元素環状化合物 / 合成 / 複素環化合物 / 有機元素化学 / 有機金属化学 / 講演 / 公開シンポジウム / 学術書出版 / オキシム / Bラクタム / 触媒反応 / カルボニルイリド / メタラサイクル / 含窒素複素環化合物 / ピントナキシン / 金属含有1,3-双極子 / βラクタム
Research Abstract

特定領域研究「多元素環状化合物の創製」では,計画班員25名,公募班員110余名にのぼる研究者が集結し,多方面にわたる成果を挙げることができた。従来複素環化合物と呼ばれていたN,S,Oを含む環状化合物に加え,P,Siから各種金属元素に至るまでの多種の元素を含んだ環状化合物群(多元素環状化合物)の革新的な合成法や多段階合成戦略の開発を検討するとともに,これら化合物の反応性を総合的な見地から調べることを目的とし研究を行った。有機化学と元素化学や有機金属化学の融合分野ともいえる多元素環状化合物を機軸として,現代社会の基盤を支える物質合成に多くの可能性を提供すると同時に,従来の複素環化合物の枠を越えた我が国発の新研究領域として,その成果を広く世界に発信した。
本課題では,これらの成果を総括し取りまとめ,関連する研究者に情報提供すると同時に,広く社会に対してこれを公表した。具体的には,取りまとめ公開シンポジウムを平成16年9月16日に東京大学弥生講堂にて開催し,班員のみならず関連する研究者を一同に集め,本特定領域研究の主要な成果を社会に対してまとまった形で公表した。ここでは,3名の外国人の特別講演者に加え,本特定領域研究に積極的に採択した多くの若手研究者の中から4名を選び,講演を行った。また社会に対するもうひとつの公表手段として、主たる研究成果を学術書にまとめた。編集方針として,現在重要と考えられるトピックスに焦点をしぼり,その研究の背景,問題点や今後の展望等を含む内容とすることで,関連する研究者ばかりでなく,教育の面からも広く利用できる学術書とすることを掲げ,内容を充分吟味して出版した。このように,本特定領域研究で得られた成果を公開シンポジウムや学術書の形で,広く関連研究者,さらには社会に向かって公開・周知したことは,今後のこの分野のさらなる発展に大きく寄与する。

Report

(5 results)
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (57 results)

All 2005 Other

All Book (1 results) Publications (56 results)

  • [Book] 最新有機合成化学 ヘテロ原子・遷移金属化合物を用いる合成2005

    • Author(s)
      奈良坂紘一, 岩澤伸治 編
    • Total Pages
      194
    • Publisher
      東京化学同人
    • Related Report
      2004 Annual Research Report
  • [Publications] M.Nakamura, M.Yamane, H.Sakurai, K.Narasaka: "Preparation of Furans by Palladium-Catalyzed Reaction of Acylchromates and Propargylic Tosylates"Heterocycles. 59. 333-345 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Zaman, M.Kitamura, K.Narasaka: "Synthesis of Polycyclic Imines by Palladium-Catalyzed Domino Cyclization of Di- and Trienyl Ketone O-Pentafluorobenzoyloximes"Bull.Chem.Soc.Jpn.. 76巻. 1055-1062 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Kitamura, S.Chiba, K.Narasaka: "Synthesis of Primary Amines and N-Methylamines by the Electrophilic Amination of Grignard Reagents with 2-Imidazolidinone O-Sulfonyloxime"Bull.Chem.Soc.Jpn.. 76巻. 1063-1070 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Yoshida, M.Kitamura, K.Narasaka: "Synthesis of Dihydropyrrole and Pyrrole Derivatives by Radical Cyclization of γ,δ-Unsaturated Ketone O-Acetyloximes."Bull.Chem.Soc.Jpn.. 76巻. 2003-2008 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Yanagisawa, K.Miura, M.Kitamura, K.Narasaka: "Intramolecular Substitution Reaction of Lithium Alkylidene Carbeniods. Regioselective Synthesis of Indenes"Bull.Chem.Soc.Jpn.. 76. 2009-2026 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Kitamura, M.Yoshida, T.Kikuchi, K.Narasaka: "Synthesis of Quinolines and 2H-Dihydropyrroles by Nucleophilic Substraction at the Nitrogen Atom of Oxime Derivatives"Synthesis. 2003. 2415-2426 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Murakami, S.Hori: "Ruthenium-Mediated Regio- and Stereoselective Alkenylation of Pyridine"J.Am.Chem.Soc.. 125. 4720-4721 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Suginome, A.Yamamoto, M.Murakami: "Palladium- and Nickel-Catalyzed Intramolecular Cyanoboration of Alkynes"J.Am.Chem.Soc.. 125. 6358-6359 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Suginome, T.Ohmura, Y.Miyake, S.Mitani, Y.Ito, M.Murakami: "Enantioface-Selective Palladium-Catallyzed Silaboration of Allenes via Double Asymmetric Induction"J.Am.Chem.Soc.. 125. 11174-11175 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Murakami, M.Hasegawa, H.Igawa: "Theoretical and Experimental Studies on the Thermal Ring Opening Reaction of Cyclobutene Having a Stannyl Substituent at the 3-Position"J.Org.Chem.. 69. 587-590 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Miura, K.Kiyota, H.Kusama, K.Lee, H.Kim, S.Kim, P.H.Lee, N.Iwasawa: "W(CO)_5(L)-Catalyzed Endo-Selective Cyclization of Allenyl Silyl Enol Ethers : An Efficient Method for the Cyclopentene Annulation onto α,β-Unsaturated Ketones,"Org.Lett.. 5. 1725-1728 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Lee, H.Kim, T.Miura, K.Kiyota, H.Kusama, S.Kim, N.Iwasawa, P.H.Lee: "Indium-Mediated β-Allylation, β-Propargylation, and β-Allenylation onto α,β-Unsaturated Ketones : Reactions of in-Situ-Generated 3- tert-Butyldimethylsillyloxyalk-2-enylsulfonium Salts with in-Situ-Generated Organoindium Reagents,"J.Am.Chem.Soc.. 125. 9682-9688 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] J.Takaya, H.Kusama, N.Iwasawa: "Isolation and Reaction of (Indolin-3-ylidene)pentacarbonyltungsten Generated from Tungsten-Containing Azomethine Ylide"Chem.Lett.. 33. 16-17 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Kusama, H.Funami, J.Takaya, N.Iwasawa: "Platinum(II)-Catalyzed Reaction of 2-Alkynylbenzoates or Benzothioates with Vinyl Ethers : A Concise Method for Synthesis of 1-Acyl-4-alkoxy- or 1 -Acyl-4-alkylsulfanyl-naphthalene Derivatives"Org.Lett.. 6. 605-608 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Nakajima, T.Yokota, M.Saito, S.Hashimoto: "Enantioselective Aldol Reactions of Trichlorosilyl Enol Ethers Catalyzed by Chiral N, N'-dioxides and Monodentate N-oxides"Tetrahedron Lett.. 45. 61-64 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Nakamura, Y.Hirata, T.Kurosaki, M.Anada, O.Kataoka, S.Kitagaki, S.Hashimoto: "Total Synthesis of the Squalene Synthase Inhibitor Zaragozic Acid C by a Carbonyl Ylide Cycloaddition Strategy"Angew.Chem., Int.Ed.. 42. 5351-5355 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Nakajima, S.Yamamoto, Y.Yamaguchi, S.Nakamura, S.Hashimoto: "Enantioselective Michael Additions of β-Keto Esters to α,β-Unsaturated Carbonyl Compounds Catalyzed by a Chiral Biquinoline N, N'-dioxide-Scandium Trifluoromethanesulfonate Complex,"Tetrahedron. 59. 7307-73** (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Tsutsui, Y.Yamaguchi, S.Kitagaki, S.Nakamura, M.Anada, S.Hashimoto: "Dirhodium(II) Tetrakis[N-tetrafluorophthaloyl-(S)- tert-leucinate] : an Exceptionally Effective Rh(II) Catalyst for Enantiotopically Selective Aromatic C-H Insertions of Diazo Ketoesters,"Tetrahedron Asym.. 14. 817-821 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Koganemaru Y, Kitamura M, Narasaka K: "Synthesis of dihydropyrrole derivatives by copper-catalyzed cyclization of γ,δ-unsaturated ketone O-methoxycarbonyloximes"Chem. Lett.. 8号. 784-785 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Tsutsui H, Kitamura M, Narasaka K: "Synthesis of pyrrole derivatives by palladium-catalyzed cyclization of γ,δ-unsaturated ketone O-pentafluorobenzoyloximes"Bull. Chem. Soc. Jpn.. 75巻7号. 1451-1460 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Kitamura M, Chiba S, Saku O, Narasaka K: "Palladium-catalyzed synthesis of 1-azaazulenes from cycloheptatrienylmethyl ketone O-pentafluorobenzoyl oximes"Chem. Lett.. 6号. 606-607 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Narasaka K: "Metal-assisted amination with oxime derivatives"Pure Appl. Chem.. 74巻1号. 143-149 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Yoshida M, Kitamura M, Narasaka K: "Synthesis of 3,4-dihydro-2H-pyrroles from gamma, delta-unsaturated ketone O-acetyloximes"Chem. Lett.. 2号. 144-145 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Yanagisawa H, Miura K, Kitamura M, Narasaka K, Ando K: "Intramolecular substitution reaction of alkylidene-lithium carbenoids : Regioselective synthesis of indenes"Helv. Chim. Acta.. 85巻10号. 3130-3135 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Saito, H.Oishi, S.Kitagaki, S.Nakamura, M.Anada, S.Hashimoto: "Enantio-and Diastereoselective Synthesis of cis-2-Aryl-3-methoxycarbonyl-2,3-dihydrobenzofurans via the Rh-(II)-Catalyzed C-H Insertion Process"Org. Lett.. 4号. 3887-3890 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Yamawaki, H.Tsutsui, S.Kitagaki, M.Anada, S.Hashimoto: "Dirhodium(II) Tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate] : a New Chiral Rh(II) Catalyst for Enantioselective Amidation of C-H Bonds"Tetrahedron Lett.. 43巻. 9561-9564 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Nakamura, J.Inagaki, M.Kudo, T.Sugimoto, K.Obara, M.Nakajima, S.Hashimoto: "Studies Directed toward the Total Synthesis of Pinnatoxin A : Synthesis of the 6,5,6-Dispiroketal (BCD Ring) System by Double Hemiketal Formation/Hetero-Michael Addition Strategy"Tetrahedron. 58巻. 10353-10374 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Nakamura, J.Inagaki, T.Sugimoto, Y.Ura, S.Hashimoto: "A Highly Stereoselective Synthesis of the C10-C31 (BCDEF Ring) Portion of Pinnatoxin A"Tetrahedron. 58巻. 10375-10386 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Murakami, T.Itahashi, Y.Ito: "Catalyzed Intramolecular Olefin Insertion into a CarbonCarbon Single Bond"J. Am. Chem. Soc.. 124号. 13976-13977 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Murakami, H.Igawa, Y.Ito: "Rhodium-catalysed Addition of Arylboronic Acids to Oxabenzonorbornadienes"Chem. Commun.. 390-391 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Murakami, M.Ubukata, Y.Ito: "Ruthenium-Mediated Domino Sequence FormingSix-Membered Ring Diene from Ene-Yne and Alkene"Chem. Lett. 294-295 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Murakami, H.Igawa: "A Study on the Stereochemical Course of b-Oxygen Elimination with a Rhodium(I) complex"Helv. Chim. Acta. 85巻. 4182-4188 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Kusama, Y.Shiozawa, M.Shido, N.Iwasasa: "Tandem Cyclizations of Benzopyranylidenetungsten(0) Complexes with Electron-Rich Dienes for the Stereoselective Synthesis of Polycyclic Carbon Skeletons"Chem. Lett.. 124-125 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Kusama, H.Yamabe, N.Iwasawa: "W(CO)_5-Amine Catalyzed Exo-and Endo-Selective Cyclizations of w-Alkynyl Silyl Enol Ethers : A Highly Useful Method for the Construction of Polycyclic Compounds"Org. Lett.. 4巻. 2569-2571 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Kusama, J.Takaya, N.Iwasawa: "A Facile Method for the Synthesis of Polycyclic Indole Derivatives : The Generation and Reaction of Tungsten-Containing Azomethine Ylides"J. Am. Chem. Soc.. 124. 11592-11593 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] N.Iwasawa, T.Miura, K.Kiyota, H.Kusama, K.Lee, P.H.Lee: "An Efficient Method for the Cyclopentene Annulation onto a, b-Unsaturated Ketones : W(CO)_5(L)Catalyzed 5-Endo-Dig Cyclization of 6-Siloxy-5-en-1-ynes"Org. Lett.. 4巻. 4463-4466 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Kitamura, M., Zaman, S., Narasaka, K.: "Synthesis of spiro imines from grimes by palladinm-catalyzed cascade reaction"Synlett. 974-976 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Mikami, T., Narasaka, K.: "Photochemical transformation of gamma, delta-unsaturated ketone O-(p-cyanophenyl)oximes to 3, 4-dihydro-2H-pyrrole derivatives"Comptes Rendus Acad. Sci. Ser. II C. 4. 477-485 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Ono, A., Narasaka, K.: "Synthesis of alpha-carbolines from beta-(3-Indolyl) ketone 0-2,4-dinitrophenyloximes"Chem. Lett.. 146-147 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tsutsui, H., Narasaka, K: "Synthesis of pyridine and isoquinoline derivatives by the palladium-catalyzed cyclization of olefinic ketone O-pentafluorobenzoyloximes"Chem. Lett.. 526-527 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Kitagaki, Y.Yamamoto, H.Okubo, M.Nakajima., S.Hashimoto: "Enantiocontrol in Tandem Allylic Sulfonium Ylide Generation and [2,3]-Sigmatropic Rearrangement Catalyzed by Chiral Dirhodium(II) Complexes"Heterocycles. 54. 623-628 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Takahashi, H.Tsutsui, M.Tamura, M.Nakajima, S.Hashimoto: "Catalytic Asymmetric Synthesis of 1,1-Spirobiindan-3,3-dione via a Double Intramolecular C-H Insertion Process"Chem. Commun. 1604-1605 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Kitagaki, Y.Yanamoto, M.Anada, M.Nakajima, S.Hashimoto: "Enantioselective [2,3]-Sigmatropic and [1,2]-Stevens Rearrangements viaIntramolecular Formation of Allylic Oxonium Ylides Catalyzed by ChiralDirhodium(II) Carboxylates"Tetrahedron Lett.. 42. 6361-6364 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Nakamura, J.Inagaki, T.Sugimoto, M.Kudo, M.Nakajima, S.Hashimoto: "A Stereoselective Synthesis of the C10-C31 (BCDEF Ring) Portion of Pinnatoxin A"Org. Lett.. 3. 4075-4078 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Murakami, H.Igawa: "Rhodium-Catalysed Addition of Arylboronic Acids to Oxabenzonorbornadienes"Chem. Commun. 390-391 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Murakami, Y.Miyamoto, Y.Ito: "Stereoselective Synthesis of Isomeric Functionalized 1,3-Dienes from Cyclobutenones"J. Am. Chem. Soc.. 123. 6441-6442 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Murakami, Y.Miyamoto, Y.Ito: "A Silyl Substituent Can Dictate a Concerted Electrocyclic Pathway : Inward Torquoselectivity in the Ring Opening of 3-Silyl-1-cyclobutene"Angew. Chem. Int. Ed.. 40. 189-190 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] N.Iwasawa, M.Shido, H.Kusama: "Generation and Reaction of Metal-Containing Oxonium Ylides : Tandem [3+2]-Cycloaddition-Carbene Insertion Leading to Novel Polycyclic Compounds"J. Am. Chem. Soc.. 123. 5814-5815 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] N.Iwasawa, K.Maeyama, H.Kusama: "A Novel Reaction for Annulation onto-Unsaturated Ketones : W(CO)_5・L Promoted Exo and Endo Selective Cyclizations of-Acetylenic Silyl Enol Ethers Prepared by 1,4-Addition of Propargyl Malonate to Enones"Organic Letters. 3. 3871-3873 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Miura, N.Iwasawa: "Reactions of Iodinated Vinylidene Complexes Generated from 1-Iodo-1-alkynes and W(CO)_5・THF"J. Am. Chem. Soc.. 124. 518-519 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] 奈良坂紘一 他2名: "Synthesis of Dihydropyrroles and Tetrahydropyridines by Cyclization of O-Methylsulfonyloximes Having an Active Methylene Group"Heterocycles. 52. 681-691 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 奈良坂紘一 他1名: "Synthesis of α-Carbolines from β-(3-Indolyl) Ketone O-2,4-Dinitrophenyloximes"Chem.Lett.. 146-147 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 橋本俊一 他4名: "Enantioselective intermolecular 1,3-dipolar cycloaddition via ester-derived carbonyl ylide formation catalyzed by chiral dirhodium(II) carboxylates,"Tetrahedron Lett.,. 41. 5931-5935 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 村上正浩 他2名: "A Silyl Substituent Can Dictate a Concerted Electrocyclic Pathway : Inward Torquoselectivity in the Ring Opening of 3-Silyl-1-cyclobutene"Angew.Chem.,Int.Ed.. 40. 189-190 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 村上正浩 他2名: "Lactone Formation by Rhodium-Catalyzed C-C Bond Cleavage of Cyclobutanone"Angew.Chem.,Int.Ed.. 39. 2484-2486 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 岩澤伸治 他3名: "Novel Synthesis of Pentacarbonylbenzopyranylidenetungsten(O)Complexes and their Diels-Alder Reaction with Electron-Rich Alkenes"J.Am.Chem.Soc.. 122. 10226-10227 (2000)

    • Related Report
      2000 Annual Research Report

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Published: 2001-04-01   Modified: 2018-03-28  

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