1996 年度実績報告書

希土類錯体の反応特性の解明と合成化学への新展開

研究課題

研究課題/領域番号	06241108
研究機関	九州大学
研究代表者	稲永純二九州大学, 有機化学基礎研究センター, 助教授 (50091244)
研究分担者	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) 藤原祐三九州大学, 工学部, 教授 (10029481)
キーワード	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
研究概要	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。

研究成果

(41件)

すべてその他

すべて文献書誌 (41件)

[文献書誌] 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)
[文献書誌] 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)
[文献書誌] Yoshikazu Makioka: "Isomerization of Terminal Alkynes Catalyzed by Ytterbium(II)-Aromatic Imine Complexes" Bull.Soc.Chim.Fr.(印刷中). (1997)
[文献書誌] 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)
[文献書誌] Shu Kobayashi: "Facile Synthesis of α-Amino Nitriles Using Lanthanide Triflate as a Lewis Acid Catalyst" Synlett. (印刷中). (1997)
[文献書誌] Hiroaki Sasai: "A New Practical Preparation Method for Lanthanum-Lithium-Binaphthol Catalysts(LLBs)for Use in Asymmetric Nitroaldol Reactions" Enantiomer. (印刷中). (1997)
[文献書誌] Masahiro Bougauchi: "Catalytic Asymmetric Epoxidation of α,β-Unsaturated Ketones Promoted by Lanthanoid Complexes" J.Am.Chem.Soc.(印刷中). (1997)
[文献書誌] Shu Kobayashi: "Aldehydes vs.Aldimines.Unprecedented Reactivity in their Enolate Addition Reactions" J.Org.Chem.(印刷中). (1997)
[文献書誌] 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)
[文献書誌] Harald Groger: "First Catalytic Asymmetric Hydrophosphonylation of Cyclic Imines:Highly Efficient Enantioselective Approach to a 4-Thiazolidinylphosphonate………" Tetrahedron Lett.37・52. 9291-9292 (1996)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] Won-Sup Kim: "β-Selective Glycosylation with α-Mannosyl Fluorides Using Tin(II)Triflate and Lanthanum Perchlorate" Tetrahedron Lett.37・43. 7797-7800 (1996)
[文献書誌] 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)
[文献書誌] Takeshi Hanamoto: "Ytterbium(III)Triflate-Catalyzed Selective Methanolysis of Methoxyacetates:A New Deprotective Method" J.Org.Chem.61・13. 4491-4492 (1996)
[文献書誌] Shu Kobayashi: "A Polymer-Supported Scandium Catalyst" J.Org.Chem.61・7. 2256-2257 (1996)
[文献書誌] Haruro Ishitani: "New Reactions of Imines with AlkynylSulfides Affording α,β-Unsaturated Thioimidates" J.Org.Chem.61・6. 1902-1903 (1996)
[文献書誌] 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)
[文献書誌] Tamon Okano: "Cyclodimerization of α,β-Unsaturated Ketones Catalyzed by Lanthanoid Tri-2-propoxides" Chem.Lett.9. 1041-1042 (1996)
[文献書誌] Ttsuneo Imamoto: "Methylene Insertion Reactions of Samarium Carbenoids into Boron-Hydrogen and Phosphorus-Hydrogen Bonds" Chem.Lett.8. 705-706 (1996)
[文献書誌] Atsuishi Kawada: "Ln(OTf)_3-LiC1O4 as Reusable Catalyst System for Friedel-Crafts Acylation" .Chem.Soc.,Chem.Commun.2. 183-184 (1996)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] Shu Kobayashi: "Catalytic Direct C-Acylation of Phenol and Naphthol Derivatives Using Carboxylic Acids as Acylating Reagents" Tetrahedron Lett.37・24. 4183-4186 (1996)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] 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)
[文献書誌] Shu Kobayashi: "Rare Earth Metal Complexes as Water-Tolerant Lewis Acid Catalysts in Organic Synthesis" Russ.Zhurn.Org.Khim.32. 214-222 (1996)
[文献書誌] 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)
[文献書誌] Yoshikazu Makioka: "Ytterbium(II)-Aromatic Imine Dianion Complex-Catalyzed Isomerization of Terminal Alkynes" Chem.Lett.1. 27-28 (1995)
[文献書誌] 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),
[文献書誌] 稲永純二: "希土類の科学" 化学同人(印刷中),
[文献書誌] 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),
[文献書誌] 藤原祐三: "有機金属化学入門" 朝倉書店(印刷中),
[文献書誌] 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),
[文献書誌] 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),
[文献書誌] 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),

1996 年度 実績報告書

希土類錯体の反応特性の解明と合成化学への新展開

研究代表者

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

研究成果

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] Yoshikazu Makioka: "Isomerization of Terminal Alkynes Catalyzed by Ytterbium(II)-Aromatic Imine Complexes" Bull.Soc.Chim.Fr.(印刷中). (1997)

[文献書誌] 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)

[文献書誌] Shu Kobayashi: "Facile Synthesis of α-Amino Nitriles Using Lanthanide Triflate as a Lewis Acid Catalyst" Synlett. (印刷中). (1997)

[文献書誌] Hiroaki Sasai: "A New Practical Preparation Method for Lanthanum-Lithium-Binaphthol Catalysts(LLBs)for Use in Asymmetric Nitroaldol Reactions" Enantiomer. (印刷中). (1997)

[文献書誌] Masahiro Bougauchi: "Catalytic Asymmetric Epoxidation of α,β-Unsaturated Ketones Promoted by Lanthanoid Complexes" J.Am.Chem.Soc.(印刷中). (1997)

[文献書誌] Shu Kobayashi: "Aldehydes vs.Aldimines.Unprecedented Reactivity in their Enolate Addition Reactions" J.Org.Chem.(印刷中). (1997)

[文献書誌] 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)

[文献書誌] Harald Groger: "First Catalytic Asymmetric Hydrophosphonylation of Cyclic Imines:Highly Efficient Enantioselective Approach to a 4-Thiazolidinylphosphonate………" Tetrahedron Lett.37・52. 9291-9292 (1996)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] Won-Sup Kim: "β-Selective Glycosylation with α-Mannosyl Fluorides Using Tin(II)Triflate and Lanthanum Perchlorate" Tetrahedron Lett.37・43. 7797-7800 (1996)

[文献書誌] 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)

[文献書誌] Takeshi Hanamoto: "Ytterbium(III)Triflate-Catalyzed Selective Methanolysis of Methoxyacetates:A New Deprotective Method" J.Org.Chem.61・13. 4491-4492 (1996)

[文献書誌] Shu Kobayashi: "A Polymer-Supported Scandium Catalyst" J.Org.Chem.61・7. 2256-2257 (1996)

[文献書誌] Haruro Ishitani: "New Reactions of Imines with AlkynylSulfides Affording α,β-Unsaturated Thioimidates" J.Org.Chem.61・6. 1902-1903 (1996)

[文献書誌] 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)

[文献書誌] Tamon Okano: "Cyclodimerization of α,β-Unsaturated Ketones Catalyzed by Lanthanoid Tri-2-propoxides" Chem.Lett.9. 1041-1042 (1996)

[文献書誌] Ttsuneo Imamoto: "Methylene Insertion Reactions of Samarium Carbenoids into Boron-Hydrogen and Phosphorus-Hydrogen Bonds" Chem.Lett.8. 705-706 (1996)

[文献書誌] Atsuishi Kawada: "Ln(OTf)_3-LiC1O4 as Reusable Catalyst System for Friedel-Crafts Acylation" .Chem.Soc.,Chem.Commun.2. 183-184 (1996)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] Shu Kobayashi: "Catalytic Direct C-Acylation of Phenol and Naphthol Derivatives Using Carboxylic Acids as Acylating Reagents" Tetrahedron Lett.37・24. 4183-4186 (1996)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] 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)

[文献書誌] Shu Kobayashi: "Rare Earth Metal Complexes as Water-Tolerant Lewis Acid Catalysts in Organic Synthesis" Russ.Zhurn.Org.Khim.32. 214-222 (1996)

[文献書誌] 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)

[文献書誌] Yoshikazu Makioka: "Ytterbium(II)-Aromatic Imine Dianion Complex-Catalyzed Isomerization of Terminal Alkynes" Chem.Lett.1. 27-28 (1995)

[文献書誌] 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),

[文献書誌] 稲永純二: "希土類の科学" 化学同人(印刷中),

[文献書誌] 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),

[文献書誌] 藤原祐三: "有機金属化学入門" 朝倉書店(印刷中),

[文献書誌] 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),

[文献書誌] 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),

[文献書誌] 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),

1996 年度実績報告書

稲永純二九州大学, 有機化学基礎研究センター, 助教授 (50091244)

[文献書誌] 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),