1998 年度実績報告書

高次構造構築法の開発

研究課題

研究課題/領域番号	08245101
研究機関	東京大学
研究代表者	奈良坂紘一東京大学, 大学院・理学系研究科, 教授 (50016151)
研究分担者	宮下正昭北海道大学, 大学院・理学研究科, 教授 (50006326) 冨士薫京都大学, 化学研究所, 教授 (20027056) 橋本俊一北海道大学, 薬学部・総合薬学科, 教授 (80107391) 竜田邦明早稲田大学, 大学院・理工学研究科, 教授 (40051627) 北泰行大阪大学, 薬学部, 教授 (00028862)
キーワード	オキシム窒素原子上での置換反応 / 不斉分子内C-H挿入反応 / 超原子価ヨウ素化合物 / 不斉1,3双極環化反応 / 不斉ニトロオレフィン化反応
研究概要	本研究では,現在その生理活性や特異的な構造が注目を集めている代表的な高次構造天然有機化合物を視野におき,これらの化合物の基本炭素骨格の構築,あるいはその立体化学の制御を可能とする新しい合成手法を開発することを目的とし研究を行った。本年度はその最終年度であり,各班員がこれまでの成果をもとに,高次構造天然化合物の合成を検討した。具体的な成果を以下に示す。・オキシム窒素原子上での置換反応を含窒素複素環化合物の合成法として確立し,これを利用して,Xenovenineの全合成を達成した。・エポキシアシラートの骨格転位反応と,多環性化合物間のDiels-Alder反応を鍵反応として,Fredericamycinの不斉全合成を達成した。また,超原子価ヨウ素試薬によるキノンイミン合成反応をもとに,Makaluvamineの全合成にも成功した。・新しい15員環形成反応を開発し抗HIV活性を有する(+)-Terpestacinの全合成を達成した。・キラルなロジウム(II)錯体触媒を用い不斉分子内C-H挿入反応を実現し,ホスホジエステラーゼ阻害剤の全合成に成功した。またカルボニルイリドの不斉1,3双極子環化反応を実現し,これを用いてZaragozic Acidのコア部分の立体選択的な合成を行った。・不斉ニトロオレフィン化反応を確立し,これを用いてSpirotryptostatin Bの基本骨格の構築を行った。・γ,δ-エポキシアクリル酸エステルを利用した不斉第四級炭素構築法をもとに,Scytophycin Cの合成を検討した。・mRNAのプロセッシングに必要な3'部位がbiotin標識されたU1RNAの5'末端部位の合成を行い,これを活用して核膜透過シグナルタンパクの単離同定に成功した。・酒石酸エステルを不斉源として用いる不斉1,3-双極子付加環化反応を利用して,Lasubine IIの合成を行った。

研究成果
(24件)

すべてその他

すべて文献書誌 (24件)

[文献書誌] 奈良坂紘一: "Synthesis of Dihydropyrroles and Tetrahydropyridines by the Intramolecular Cyclization of θ-Methylsulfonyloximes Having an Active Methine Group" Chem.Lett.607-608 (1998)
[文献書誌] 奈良坂紘一: "Synthesis of Dihydropyrroles by the Intramolecular Addition of Alkyldeneaminyl Radicals Generated from θ-2,4-Dinitrophenyloximes of γ,δ-Unsaturated Ketones" Chem.Lett.1261-1262 (1998)
[文献書誌] 奈良坂紘一: "Synthesis of Pyrrole Derivatives by the Heck-Type Cyclization of γ,δ-Unsaturated Ketone θ-Pentrafluorobenzoyloximes" Chem.Lett.45-46 (1999)
[文献書誌] 北泰行: "An Efficient Synthesis of peri-Hydroxy Aromatic Compounds: A Strong Base-Induced [4+2]Cycloaddition of 4-Phenylthio-Substituted Homophthalic Anhydrides with Various Sulfinyl-Substituted Dienophiles" Synlett. 292- (1998)
[文献書誌] 北泰行: "A Novel and Direct a-Azidation of Cyclic Sulfides Using a Hypervalent Iodine(III)Reagent" Chem.Commun.143- (1998)
[文献書誌] 北泰行: "A Novel and Efficient Synthesis of Pyrroloiminoquinone Using a Hypervalent Iodine(III)Reagent" J.Chem.Soc.,Perkin Trans 1. 635- (1998)
[文献書誌] 関根光雄: "Chemical synthesis and properties of conformationally fixed diuridine monophosphates as building blocks of RNA turn motif" J.Org.Chem.63. 1429-1443 (1998)
[文献書誌] 関根光雄: "Snurportin 1,an m3G-cap-specific nuclear import receptor with a novel domain structure" EMBO J.17. 4114-4126 (1998)
[文献書誌] 関根光雄: "Synthesis of new aminoacyl-adenylate analogs having an N-acyl phosphoramidate linkage" Tetrahedron Lett.39. 3725-3728 (1998)
[文献書誌] 竜田邦明: "The first total synthesis of a bioxanthracene (-)-ES-242-4,an N-methyl-D-aspartate receptor antagonist" Tetrahedron Lett.39. 1771-1774 (1998)
[文献書誌] 竜田邦明: "Synthesis and biological evaluation of the analogs of bioxanthracenes ES-242s,N-methyl-D-aspartate antagonists" J.Antibiot.51(3). 383-386 (1998)
[文献書誌] 竜田邦明: "The first total synthesis of natural (+)-terpestacin,Syncytium formation inhibitor" J.Antibiot.51(6). 602-606 (1998)
[文献書誌] 橋本俊一: "Enantioselective Synthesis of 4-Substituted 2-Pyrrolidinones by Site-selective C-H Insertion of a-Methoxycarbonyl-a-diazoacetanilides Catalyzed by Dirhodium(II) Tetrakis [N-phthaloy-(S)tert-leucinate]" Tetrahedron Lett.39. 79-82 (1998)
[文献書誌] 橋本俊一: "Toward the Second-Generation Synthesis of Zaragozic Acids : Construction of the 2,8-Dioxabicyclo[3.2.1]octane Core System via Tandem Carbonyl Ylide Formation and 1,3-Dipolar Cycloaddition Sequence" Tetrahedron Lett.39. 2371-2374 (1998)
[文献書誌] 橋本俊一: "Enantioselective Intramolecular C-II Insertion Route to a Key Intermediate for the Synthesis of Trinem Antibiotics" Tetrahedron Lett.39. 9063-9066 (1998)
[文献書誌] 冨士薫: "Enantioselective Creation of Quartenary Carbon Centers through Addition-Elimination Reaction" Heterocycles. 47. 951-964 (1998)
[文献書誌] 冨士薫: "The First Synthesis of an Optically Active Molecular Bevel Gear with Only Two Cogs on Each Wheel" Tetrahedron Lett.39. 1373-1376 (1998)
[文献書誌] 冨士薫: "Palladium-Catalyzed Asymmetric Reduction of Allylic Esters with a New Chiral Mondentate Ligard,8-Diphenylphosphosphino-8'-methoxy-1,1'-binaphthyl" Tetrahedron Lett.39. 6323-6326 (1998)
[文献書誌] 宮下正昭: "Effficient and Stereospecific Construction of Asymmetric Quaternary Carbons via g-Alkyl-g,d-epoxy Acrylates" Tetrahedron Lett.39. 3775-3778 (1998)
[文献書誌] 宮下正昭: "Highly Stereoselective Epoxidation of a 4-Methyl-5(triethylsilyl) oxyallyl Alcohol System with m-Chloroperoxybenzoic Acid" Tetrahedron Lett.39. 4517-4520 (1998)
[文献書誌] 宮下正昭: "Expeditious and Stereoselective Synthesis of Chiral trans b-Hydroxy-d-lactone Systems" Chem.Lett.109-110 (1998)
[文献書誌] 猪股勝彦: "Enantio-and Diastereoselective Synthesis of Isoxazolidines by Asymmetric 1,3-DIpolar Cycloaddition of Nitrones" Chem.Lett.547-548 (1997)
[文献書誌] 猪股勝彦: "酒石酸エステルを活用する不斉付加環化反応および不斉求核付加反応" 有機合成化学協会誌. 56. 11-21 (1998)
[文献書誌] 猪股勝彦: "Development of New Asymmetric Reactions Utilizing Tartaric Acid Ester as a Chiral Auxiliary : Design of an Efficient Chiral Dinucleating System" Review on Heteroatom Chemistry. 18. 119-140 (1998)

1998 年度 実績報告書

高次構造構築法の開発

研究代表者

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

研究成果

[文献書誌] 奈良坂 紘 一: "Synthesis of Dihydropyrroles and Tetrahydropyridines by the Intramolecular Cyclization of θ-Methylsulfonyloximes Having an Active Methine Group" Chem.Lett.607-608 (1998)

[文献書誌] 奈良坂 紘 一: "Synthesis of Dihydropyrroles by the Intramolecular Addition of Alkyldeneaminyl Radicals Generated from θ-2,4-Dinitrophenyloximes of γ,δ-Unsaturated Ketones" Chem.Lett.1261-1262 (1998)

[文献書誌] 奈良坂 紘 一: "Synthesis of Pyrrole Derivatives by the Heck-Type Cyclization of γ,δ-Unsaturated Ketone θ-Pentrafluorobenzoyloximes" Chem.Lett.45-46 (1999)

[文献書誌] 北 泰行: "An Efficient Synthesis of peri-Hydroxy Aromatic Compounds: A Strong Base-Induced [4+2]Cycloaddition of 4-Phenylthio-Substituted Homophthalic Anhydrides with Various Sulfinyl-Substituted Dienophiles" Synlett. 292- (1998)

[文献書誌] 北 泰行: "A Novel and Direct a-Azidation of Cyclic Sulfides Using a Hypervalent Iodine(III)Reagent" Chem.Commun.143- (1998)

[文献書誌] 北 泰行: "A Novel and Efficient Synthesis of Pyrroloiminoquinone Using a Hypervalent Iodine(III)Reagent" J.Chem.Soc.,Perkin Trans 1. 635- (1998)

[文献書誌] 関根 光雄: "Chemical synthesis and properties of conformationally fixed diuridine monophosphates as building blocks of RNA turn motif" J.Org.Chem.63. 1429-1443 (1998)

[文献書誌] 関根 光雄: "Snurportin 1,an m3G-cap-specific nuclear import receptor with a novel domain structure" EMBO J.17. 4114-4126 (1998)

[文献書誌] 関根 光雄: "Synthesis of new aminoacyl-adenylate analogs having an N-acyl phosphoramidate linkage" Tetrahedron Lett.39. 3725-3728 (1998)

[文献書誌] 竜田 邦明: "The first total synthesis of a bioxanthracene (-)-ES-242-4,an N-methyl-D-aspartate receptor antagonist" Tetrahedron Lett.39. 1771-1774 (1998)

[文献書誌] 竜田 邦明: "Synthesis and biological evaluation of the analogs of bioxanthracenes ES-242s,N-methyl-D-aspartate antagonists" J.Antibiot.51(3). 383-386 (1998)

[文献書誌] 竜田 邦明: "The first total synthesis of natural (+)-terpestacin,Syncytium formation inhibitor" J.Antibiot.51(6). 602-606 (1998)

[文献書誌] 橋本 俊一: "Enantioselective Synthesis of 4-Substituted 2-Pyrrolidinones by Site-selective C-H Insertion of a-Methoxycarbonyl-a-diazoacetanilides Catalyzed by Dirhodium(II) Tetrakis [N-phthaloy-(S)tert-leucinate]" Tetrahedron Lett.39. 79-82 (1998)

[文献書誌] 橋本 俊一: "Toward the Second-Generation Synthesis of Zaragozic Acids : Construction of the 2,8-Dioxabicyclo[3.2.1]octane Core System via Tandem Carbonyl Ylide Formation and 1,3-Dipolar Cycloaddition Sequence" Tetrahedron Lett.39. 2371-2374 (1998)

[文献書誌] 橋本 俊一: "Enantioselective Intramolecular C-II Insertion Route to a Key Intermediate for the Synthesis of Trinem Antibiotics" Tetrahedron Lett.39. 9063-9066 (1998)

[文献書誌] 冨士 薫: "Enantioselective Creation of Quartenary Carbon Centers through Addition-Elimination Reaction" Heterocycles. 47. 951-964 (1998)

[文献書誌] 冨士 薫: "The First Synthesis of an Optically Active Molecular Bevel Gear with Only Two Cogs on Each Wheel" Tetrahedron Lett.39. 1373-1376 (1998)

[文献書誌] 冨士 薫: "Palladium-Catalyzed Asymmetric Reduction of Allylic Esters with a New Chiral Mondentate Ligard,8-Diphenylphosphosphino-8'-methoxy-1,1'-binaphthyl" Tetrahedron Lett.39. 6323-6326 (1998)

[文献書誌] 宮下 正昭: "Effficient and Stereospecific Construction of Asymmetric Quaternary Carbons via g-Alkyl-g,d-epoxy Acrylates" Tetrahedron Lett.39. 3775-3778 (1998)

[文献書誌] 宮下 正昭: "Highly Stereoselective Epoxidation of a 4-Methyl-5(triethylsilyl) oxyallyl Alcohol System with m-Chloroperoxybenzoic Acid" Tetrahedron Lett.39. 4517-4520 (1998)

[文献書誌] 宮下 正昭: "Expeditious and Stereoselective Synthesis of Chiral trans b-Hydroxy-d-lactone Systems" Chem.Lett.109-110 (1998)

[文献書誌] 猪股 勝彦: "Enantio-and Diastereoselective Synthesis of Isoxazolidines by Asymmetric 1,3-DIpolar Cycloaddition of Nitrones" Chem.Lett.547-548 (1997)

[文献書誌] 猪股 勝彦: "酒石酸エステルを活用する不斉付加環化反応および不斉求核付加反応" 有機合成化学協会誌. 56. 11-21 (1998)

[文献書誌] 猪股 勝彦: "Development of New Asymmetric Reactions Utilizing Tartaric Acid Ester as a Chiral Auxiliary : Design of an Efficient Chiral Dinucleating System" Review on Heteroatom Chemistry. 18. 119-140 (1998)

1998 年度実績報告書

奈良坂紘一東京大学, 大学院・理学系研究科, 教授 (50016151)

[文献書誌] 奈良坂紘一: "Synthesis of Dihydropyrroles and Tetrahydropyridines by the Intramolecular Cyclization of θ-Methylsulfonyloximes Having an Active Methine Group" Chem.Lett.607-608 (1998)

[文献書誌] 奈良坂紘一: "Synthesis of Dihydropyrroles by the Intramolecular Addition of Alkyldeneaminyl Radicals Generated from θ-2,4-Dinitrophenyloximes of γ,δ-Unsaturated Ketones" Chem.Lett.1261-1262 (1998)

[文献書誌] 奈良坂紘一: "Synthesis of Pyrrole Derivatives by the Heck-Type Cyclization of γ,δ-Unsaturated Ketone θ-Pentrafluorobenzoyloximes" Chem.Lett.45-46 (1999)

[文献書誌] 北泰行: "An Efficient Synthesis of peri-Hydroxy Aromatic Compounds: A Strong Base-Induced [4+2]Cycloaddition of 4-Phenylthio-Substituted Homophthalic Anhydrides with Various Sulfinyl-Substituted Dienophiles" Synlett. 292- (1998)

[文献書誌] 北泰行: "A Novel and Direct a-Azidation of Cyclic Sulfides Using a Hypervalent Iodine(III)Reagent" Chem.Commun.143- (1998)

[文献書誌] 北泰行: "A Novel and Efficient Synthesis of Pyrroloiminoquinone Using a Hypervalent Iodine(III)Reagent" J.Chem.Soc.,Perkin Trans 1. 635- (1998)

[文献書誌] 関根光雄: "Chemical synthesis and properties of conformationally fixed diuridine monophosphates as building blocks of RNA turn motif" J.Org.Chem.63. 1429-1443 (1998)

[文献書誌] 関根光雄: "Snurportin 1,an m3G-cap-specific nuclear import receptor with a novel domain structure" EMBO J.17. 4114-4126 (1998)

[文献書誌] 関根光雄: "Synthesis of new aminoacyl-adenylate analogs having an N-acyl phosphoramidate linkage" Tetrahedron Lett.39. 3725-3728 (1998)

[文献書誌] 竜田邦明: "The first total synthesis of a bioxanthracene (-)-ES-242-4,an N-methyl-D-aspartate receptor antagonist" Tetrahedron Lett.39. 1771-1774 (1998)

[文献書誌] 竜田邦明: "Synthesis and biological evaluation of the analogs of bioxanthracenes ES-242s,N-methyl-D-aspartate antagonists" J.Antibiot.51(3). 383-386 (1998)

[文献書誌] 竜田邦明: "The first total synthesis of natural (+)-terpestacin,Syncytium formation inhibitor" J.Antibiot.51(6). 602-606 (1998)

[文献書誌] 橋本俊一: "Enantioselective Synthesis of 4-Substituted 2-Pyrrolidinones by Site-selective C-H Insertion of a-Methoxycarbonyl-a-diazoacetanilides Catalyzed by Dirhodium(II) Tetrakis [N-phthaloy-(S)tert-leucinate]" Tetrahedron Lett.39. 79-82 (1998)

[文献書誌] 橋本俊一: "Toward the Second-Generation Synthesis of Zaragozic Acids : Construction of the 2,8-Dioxabicyclo[3.2.1]octane Core System via Tandem Carbonyl Ylide Formation and 1,3-Dipolar Cycloaddition Sequence" Tetrahedron Lett.39. 2371-2374 (1998)

[文献書誌] 橋本俊一: "Enantioselective Intramolecular C-II Insertion Route to a Key Intermediate for the Synthesis of Trinem Antibiotics" Tetrahedron Lett.39. 9063-9066 (1998)

[文献書誌] 冨士薫: "Enantioselective Creation of Quartenary Carbon Centers through Addition-Elimination Reaction" Heterocycles. 47. 951-964 (1998)

[文献書誌] 冨士薫: "The First Synthesis of an Optically Active Molecular Bevel Gear with Only Two Cogs on Each Wheel" Tetrahedron Lett.39. 1373-1376 (1998)

[文献書誌] 冨士薫: "Palladium-Catalyzed Asymmetric Reduction of Allylic Esters with a New Chiral Mondentate Ligard,8-Diphenylphosphosphino-8'-methoxy-1,1'-binaphthyl" Tetrahedron Lett.39. 6323-6326 (1998)

[文献書誌] 宮下正昭: "Effficient and Stereospecific Construction of Asymmetric Quaternary Carbons via g-Alkyl-g,d-epoxy Acrylates" Tetrahedron Lett.39. 3775-3778 (1998)

[文献書誌] 宮下正昭: "Highly Stereoselective Epoxidation of a 4-Methyl-5(triethylsilyl) oxyallyl Alcohol System with m-Chloroperoxybenzoic Acid" Tetrahedron Lett.39. 4517-4520 (1998)

[文献書誌] 宮下正昭: "Expeditious and Stereoselective Synthesis of Chiral trans b-Hydroxy-d-lactone Systems" Chem.Lett.109-110 (1998)

[文献書誌] 猪股勝彦: "Enantio-and Diastereoselective Synthesis of Isoxazolidines by Asymmetric 1,3-DIpolar Cycloaddition of Nitrones" Chem.Lett.547-548 (1997)

[文献書誌] 猪股勝彦: "酒石酸エステルを活用する不斉付加環化反応および不斉求核付加反応" 有機合成化学協会誌. 56. 11-21 (1998)

[文献書誌] 猪股勝彦: "Development of New Asymmetric Reactions Utilizing Tartaric Acid Ester as a Chiral Auxiliary : Design of an Efficient Chiral Dinucleating System" Review on Heteroatom Chemistry. 18. 119-140 (1998)