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希土類錯体の反応特性の解明と合成化学への新展開

Research Project

Project/Area Number 06241108
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionKyushu University

Principal Investigator

稲永 純二  九州大学, 有機化学基礎研究センター, 助教授 (50091244)

Co-Investigator(Kenkyū-buntansha) 笹井 宏明  東京大学, 薬学部, 助教授 (90205831)
小林 修  東京理科大学, 理学部, 助教授 (50195781)
岡野 多門  鳥取大学, 工学部, 助教授 (20112104)
今本 恒雄  千葉大学, 理学部, 教授 (10134347)
藤原 祐三 (藤原 佑三)  九州大学, 工学部, 教授 (10029481)
Project Period (FY) 1994 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥53,100,000 (Direct Cost: ¥53,100,000)
Fiscal Year 1996: ¥21,100,000 (Direct Cost: ¥21,100,000)
Fiscal Year 1995: ¥16,000,000 (Direct Cost: ¥16,000,000)
Fiscal Year 1994: ¥16,000,000 (Direct Cost: ¥16,000,000)
Keywords光学活性希土類錯体触媒 / イミン-Yb錯体 / 希土類イソプロポキシド / 高分子希土類触媒 / 不斉ヘテロDiels-Alder反応 / 希土類のルイス酸性の評価 / 触媒的脱水素シリル化反応 / 触媒的不斉エポキシ化 / サマリウムケチル / 立体選択的ラジカル反応 / ケトン-希土類(II)ジアニオン錯体 / イミン希土類(II)ジアニオン錯体 / 希土類アルコキシド / 希土類超強酸塩 / スカンジウムパ-フラート / ランタノイド(II)トリフラート / アリルサマリウム / 脱酸素的炭素-炭素結合生成反応 / アルケニルセリウム錯体
Research Abstract

1.3価の光学活性希土類錯体-Yb[(-)BNP]_3-を触媒とするヘテロDiels-Alder反応で高い不斉誘起(室温下最高93%ee)を達成するとともに、触媒に関する正の非線形効果(不斉増幅現象)を見い出した。
2.希土類では世界初のトリフェニルイミン-Yb錯体の単離・X線結晶解析に成功し、この錯体の触媒活性を検討した結果、末端アセチレンの2-アセチレンへの異性化反応および末端アセチレンの脱水素シリル化反応のよい触媒(10モル%)となることを見い出した。
3.同型の立体構造をもつ一連の希土類錯体のタンデム質量スペクトル解析により、中心希土類金属イオンの違いに基づく構造-反応性相関を評価した。希土類トリフラート・テトラヒドロ-2-ピリミドン錯体を合成し、その単結晶X線構造解析からユニークな配位構造を明らかにした。
4.希土類トリイソプロポキシドがα,β-不飽和ケトンの環化二量化反応やRobinson環化反応の良い触媒になること、また、その触媒活性が前者の反応では軽希土が、後者では重希土で高いことを明らかにした。
5.ランタノイド触媒を用いるイミン類の活性化、高分子に固定化したランタノイド触媒の合成とそれを用いる反応、およびキラルなランタノイド触媒を用いる不斉触媒反応の開発研究に重点を置き、新規合成反応、特に炭素-炭素結合生成反応の開発に成功した。
6.希土類-ビナフトール錯体を触媒として、tert-ブチルヒドロペルオキシド等を酸化剤とするエノン類の汎用性に富むエポキシ化反応の開発に成功した。反応はモレキュラーシ-ブス4Aの添加により効率よく進行し、室温下最高94%eeを達成した。

Report

(3 results)
  • 1996 Annual Research Report
  • 1995 Annual Research Report
  • 1994 Annual Research Report
  • Research Products

    (71 results)

All Other

All Publications (71 results)

  • [Publications] Takeshi Hanamoto: "Scandium(III)Perfluorooctanesulfonate[Sc(OPf)_3]:A Novel Catalyst for the Hetero Diels-Alder Reaction of Aldehydes with Non-Activated Dienes" Bull.Chem.Soc.Jpn.(印刷中). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takeshi Hanamoto: "Highly Regio-and Stereoselective Synthesis of Allylsilanes via Palladium-Catalyzed Reductive Metallation of Allylic Phosphates with…………" Bull.Soc.Chim.Fr.(印刷中). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Yoshikazu Makioka: "Isomerization of Terminal Alkynes Catalyzed by Ytterbium(II)-Aromatic Imine Complexes" Bull.Soc.Chim.Fr.(印刷中). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shu Kobayashi: "The Catalytic Fries Rearrangement and o-Acylation Reactions Using Group 3 and 4 Metal Triflates as Catalysts" Bull.Chem.Soc.Jpn.(印刷中). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shu Kobayashi: "Facile Synthesis of α-Amino Nitriles Using Lanthanide Triflate as a Lewis Acid Catalyst" Synlett. (印刷中). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Hiroaki Sasai: "A New Practical Preparation Method for Lanthanum-Lithium-Binaphthol Catalysts(LLBs)for Use in Asymmetric Nitroaldol Reactions" Enantiomer. (印刷中). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Masahiro Bougauchi: "Catalytic Asymmetric Epoxidation of α,β-Unsaturated Ketones Promoted by Lanthanoid Complexes" J.Am.Chem.Soc.(印刷中). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shu Kobayashi: "Aldehydes vs.Aldimines.Unprecedented Reactivity in their Enolate Addition Reactions" J.Org.Chem.(印刷中). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takeshi Hanamoto: "Asymmetric Hetero Diels-Alder Reaction Catalyzed by Chiral Ytterbium(III)Phosphate{Yb〔(R)-(-)-BNP〕_3}:Remarkable Ligand Effect on the Enantioselectivity" Synlett. 1. 79-81 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Harald Groger: "First Catalytic Asymmetric Hydrophosphonylation of Cyclic Imines:Highly Efficient Enantioselective Approach to a 4-Thiazolidinylphosphonate………" Tetrahedron Lett.37・52. 9291-9292 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shu Kobayashi: "Polymer Scandium-Catalyzed Three-Component Reactions Leading to Diverse Amino Ketone,Amino Ester,and Amino Nitrile Derivatives" Tetrahedron Lett.37・51. 9221-9224 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Katsuhiko Iseki: "Catalytic Asymmetric Nitroaldol Reaction of α,α-Difluoro-Aldehydes Mediated by Rare Earth-Lithium-BINOL Complexes" Tetrahedron Lett.37・50. 9081-9084 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Won-Sup Kim: "β-Selective Glycosylation with α-Mannosyl Fluorides Using Tin(II)Triflate and Lanthanum Perchlorate" Tetrahedron Lett.37・43. 7797-7800 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shu Kobayashi: "Parallel Synthesis Using Mannich-type Three-Component Reactions and Field Synthesis for the Construction of an Amino Alcohol Library" Tetrahedron Lett.37・43. 7783-7786 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takeshi Hanamoto: "Ytterbium(III)Triflate-Catalyzed Selective Methanolysis of Methoxyacetates:A New Deprotective Method" J.Org.Chem.61・13. 4491-4492 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shu Kobayashi: "A Polymer-Supported Scandium Catalyst" J.Org.Chem.61・7. 2256-2257 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Haruro Ishitani: "New Reactions of Imines with AlkynylSulfides Affording α,β-Unsaturated Thioimidates" J.Org.Chem.61・6. 1902-1903 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Tsuneo Imamoto: "Single Crystal X-Ray Analyses of a Series of Hexamethylphosphoramide-Coordinated Complexes of Rare Earth Triflates:Existence of Tetrad………" Chem.Lett.10. 875-876 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Tamon Okano: "Cyclodimerization of α,β-Unsaturated Ketones Catalyzed by Lanthanoid Tri-2-propoxides" Chem.Lett.9. 1041-1042 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Ttsuneo Imamoto: "Methylene Insertion Reactions of Samarium Carbenoids into Boron-Hydrogen and Phosphorus-Hydrogen Bonds" Chem.Lett.8. 705-706 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Atsuishi Kawada: "Ln(OTf)_3-LiC1O4 as Reusable Catalyst System for Friedel-Crafts Acylation" .Chem.Soc.,Chem.Commun.2. 183-184 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Haruro Ishitani: "Catalytic Asymmetric Aza Diels-Alder Reactions Using a Chiral Lanthanide Lewis Acid.Enantioselective Synthesis of Tetrahydroquinoline Derivatives Using………" Tetrahedron Lett.37・41. 7357-7360 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shu Kobayashi: "A New Methodology for Combinatorial Synthesis.Preparation of Diverse Quinoline Derivatives Using a Novel Polymer-Supported Scandium Catalyst" J.Am.Chem.Soc.118・37. 8977-8978 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shu Kobayashi: "Aldol Reactions on Solid Phase.Sc(OTf)_3-Catalyzed Aldol Reactions of Polymer-Supported Silyl Enol Ethers with Aldehydes Providing………" Tetrahedron Lett.37・31. 5569-5572 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Yoshikazu Makioka: "The First Isolation and Structural Characterization of a Lanthanoid-Imine Azametalla-cyclopropane Complex,[Yb(η^2-Ph_2CNPh)(hmpa)_3]" Organometallics. 15・26. 5476-5478 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Hiroaki Sasai: "Catalytic Asymmetric Michael Reactions Promoted by the La-Na-BINOL Complex(LSB).Enantioface Selection on Michael Donors" Tetrahedron Lett.37・31. 5561-5564 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shu Kobayashi: "Catalytic Direct C-Acylation of Phenol and Naphthol Derivatives Using Carboxylic Acids as Acylating Reagents" Tetrahedron Lett.37・24. 4183-4186 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shu Kobayashi: "A Novel Mannich-type Reaction:Lanthanide Triflate-Catalyzed Reactions of N-(α-Aminoalkyl)benzotriazoles with Silyl Enolates" Tetrahedron Lett.37・21. 3731-3734 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takayoshi Arai: "Self-Assembly of Heterobimetallic Complexes and Reactive Nucleophiles:A General Strategy for the Activation of Asymmetric Reactions Promoted………" Chem.Eur.J.2. 1368-1372 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shu Kobayashi: "Polymer-Supported Silyl Enol Ethers.Synthesis and Reactions with Imines for the Preparation of Amino Alcohol Library" Tetrahedron Lett.37・16. 2809-2812 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Naomichi Hashizume: "Lanthanide Triflates as Reusable Catalysts in Stereoselective α-and β-Glycosylation Reactions of 1-O-Acetyl-2,3,5-tri-O-benzylribofuranose" Carbohydr.Lett.2. 157-163 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Shu Kobayashi: "Rare Earth Metal Complexes as Water-Tolerant Lewis Acid Catalysts in Organic Synthesis" Russ.Zhurn.Org.Khim.32. 214-222 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 岡野多門: "希土類イソプロポキシドのカルボニル化合物に対する反応特性" 希土類. 29. 41-48 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Yoshikazu Makioka: "Ytterbium(II)-Aromatic Imine Dianion Complex-Catalyzed Isomerization of Terminal Alkynes" Chem.Lett.1. 27-28 (1995)

    • Related Report
      1996 Annual Research Report
  • [Publications] 稲永純二: "ランタノイドを利用する有機合成" 学会出版センター(印刷中),

    • Related Report
      1996 Annual Research Report
  • [Publications] 稲永純二: "希土類の科学" 化学同人(印刷中),

    • Related Report
      1996 Annual Research Report
  • [Publications] 藤原祐三: "ランタノイドを利用する有機合成" 学会出版センター(印刷中),

    • Related Report
      1996 Annual Research Report
  • [Publications] 藤原祐三: "有機金属化学入門" 朝倉書店(印刷中),

    • Related Report
      1996 Annual Research Report
  • [Publications] 今本恒雄: "ランタノイドを利用する有機合成" 学会出版センター(印刷中),

    • Related Report
      1996 Annual Research Report
  • [Publications] 岡野多門: "ランタノイドを利用する有機合成" 学会出版センター(印刷中),

    • Related Report
      1996 Annual Research Report
  • [Publications] 小林 修: "ランタノイドを利用する有機合成" 学会出版センター(印刷中),

    • Related Report
      1996 Annual Research Report
  • [Publications] J. Inanaga: "Achiral and Chiral Lanthanoid(III)Salts of Superacids as Novel Lewis Acid Catalysts in Organic Synthesis" New. J. Chem.19. 707-712 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Y. Sugimoto: "Plladium(o)-Samarium(II)System for the Preparation of Allenes from Propargylic Acetate. Application to the Synthesis of 2,3-Naphthoquinodimethanes" Appl. Organomet. Chem.9. 369-375 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] K. Mikami: "Palladium(o)-Catalyzed Reaction of Propargylic Phosphates with SmI_2: A Highly Regioslelective Route to the Synthesis of Allenes and Acetylenes" Tetrahedron Lett.36. 1001-1002 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Y. Makioka: "Lanthanoid Metal Promoted Reaction of Diaryl Ketones and Thioketones with Isocyanides" Chem. Lett.821-822 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Y. Taniguchi: "Lanthanoid Metal Mediated Organic Reactions of Acyltrialkylsilanes" Appl. Organomet. Chem.9. 377-384 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Y. Taniguchi: "Yb/TMSBr Promoted Homocoupling Reactions of Aliphatic Ketones, x, β-Unsaturated Ketones and Aliphatic Imines" Appl. Organomet. Chem.9. 491-503 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T. Imamoto: "Preparation and Properties of Hexamethylphosphoramide-Coordinated Complexes of Samariun(III)Iodide" Chem. Lett.949-950 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T. Imamoto: "Unusual Cerium(III) Chloride-promoted Reactions of Alkenyl Grignard Reagents or Alkenyl-lithiums with 1,3-Diphenyl-2-propanone: Formation and Trapping of......." Appl. Organomet. Chem.9. 449-456 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T. Okano: "Acetalization of Ketones and Aldehydes Catalyzed by Lanthanoid Triflluoromethylsulfonates" Appl. Organomet. Chem.9. 473-478 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T. Okano: "Transesterification Catalyzed by Lanthanoid Tri-2-propoxide" Chem. Lett.246-247 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 稲永井純二: "化学と工業" 日本化学会, 2 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 藤原祐三: "有機金属化学辞典" 朝倉書店, 47 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Y. Taniguchi: "Reviews on Heteroatom Chemistry" MYU, 16 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 藤原祐三: "触媒" 触媒学会, 14 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] J.Inanaga: "Medium-and Large-ring Formation by the Samarium(II)-Promoted Intramolecular Pinacol Couplilng Reaction" Mem.Fac.Sci.Kyushu Univ.,Ser.C. 19. 123-124 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] J.Inanaga: "Ytterbium(III) Perchlorate as a Catalytic Promoter of the Glycosylation of 1-ο-Methoxyacetyl Sugars with Alcohols" Mem.Fac.Sci.Kyushu Univ.,Ser.C. 19. 125-128 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] K.Mikami: "Palladium(0)-Catalyzed Reaction of Propargylic Phosphates with SmI_2:A Highly Regioslelective Route to the Synthesis of Allenes and Acetylenes" Tetrahedron Lett.(印刷中). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Sugimoto: "Palladium(0)-Samarium(II) System for the Preparation of Allenes from Propargylic Acetate. Application to the Synthesis of 2,3-Naphthoquinodimethanes" Appl.Organomet.Chem.(印刷中). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] J.Inanaga: "Achiral and Chiral Lanthanoid(III) Salts of Superacids as Novel Lewis Acid Catalysts in Organic Synthesis" New.J.Chem.(印刷中). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Taniguchi: "Novel Deoxygenative Acylation of Diaryl Ketones with Acylsilanes Mediated by Lanthanoid Metals" Tetrahedron Lett.35. 6897-6898 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Taniguchi: "Facile Formation of Lanthanoid(III) Thiolates from Benzophenone-Catalyzed Reaction of Lanthanoid Metals and Disulfides,and Their Use as Sulfenylating Reagents" Tetrahedron Lett.35. 7789-7792 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Taniguchi: "Lanthanoid Metal Mediated Organic Reactions of Acyltrialkylsilanes" Appl.Organomet.Chem.(印刷中). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] T.Imamoto: "Samarium(II) Iodide Promoted Reductive Ring Opening Reaction of Cyclopropane-1,1-dicarboxylic Esters. Synthesis of Substituted 5-Pentanolides from---" Tetrahedron Lett.35. 7805-7808 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] T.Imamoto: "Cerium(III) Chloride-Promoted Unusual Reactions of Alkenyl Grignard Reagents or Alkenyllithiums with 13,-Diphenyl-2-propanone. Formation and Trapping of---" Appl.Organome.Chem.(印刷中). ( 1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] T.Okano: "Acetalization of Ketones and Aldehydes Catalyzed by Lanthanoid Triflluoromethylsulfonates" Appl.Organomet.Chem.(印刷中). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] T.Okano: "Transesterification Catalyzed by Lanthanoid Tri-2-propoxide" Chem.Lett.(印刷中). (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] 稲永純二: "化学" 化学同人, 2 (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] T.Imamoto: "Lanthanides in Organic Synthesis" Academic Press, 154 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 今本恒雄: "均一系触媒反応設計のための戦略 -21世紀を担う化学者へ-" 化学同人(印刷中),

    • Related Report
      1994 Annual Research Report
  • [Publications] T.Imamoto: "Encyclopedia of Reagents for Organic Synthesis" John Wiley & Sons (印刷中),

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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