1998 Fiscal Year Annual Research Report

高次構造構築法の開発

Research Project

Project/Area Number	08245101
Research Institution	The 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)	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)
Keywords	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
Research Abstract	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。

Research Products
(24 results)

All Other

All Publications (24 results)

[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 北泰行: "A Novel and Direct a-Azidation of Cyclic Sulfides Using a Hypervalent Iodine(III)Reagent" Chem.Commun.143- (1998)
[Publications] 北泰行: "A Novel and Efficient Synthesis of Pyrroloiminoquinone Using a Hypervalent Iodine(III)Reagent" J.Chem.Soc.,Perkin Trans 1. 635- (1998)
[Publications] 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)
[Publications] 関根光雄: "Snurportin 1,an m3G-cap-specific nuclear import receptor with a novel domain structure" EMBO J.17. 4114-4126 (1998)
[Publications] 関根光雄: "Synthesis of new aminoacyl-adenylate analogs having an N-acyl phosphoramidate linkage" Tetrahedron Lett.39. 3725-3728 (1998)
[Publications] 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)
[Publications] 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)
[Publications] 竜田邦明: "The first total synthesis of natural (+)-terpestacin,Syncytium formation inhibitor" J.Antibiot.51(6). 602-606 (1998)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 冨士薫: "Enantioselective Creation of Quartenary Carbon Centers through Addition-Elimination Reaction" Heterocycles. 47. 951-964 (1998)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 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)
[Publications] 宮下正昭: "Expeditious and Stereoselective Synthesis of Chiral trans b-Hydroxy-d-lactone Systems" Chem.Lett.109-110 (1998)
[Publications] 猪股勝彦: "Enantio-and Diastereoselective Synthesis of Isoxazolidines by Asymmetric 1,3-DIpolar Cycloaddition of Nitrones" Chem.Lett.547-548 (1997)
[Publications] 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)
[Publications] 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 Fiscal Year Annual Research Report

高次構造構築法の開発

Principal Investigator

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

Research Products

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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)

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

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

[Publications] 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)

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

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

[Publications] 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)

[Publications] 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)

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

[Publications] 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)

[Publications] 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)

[Publications] 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)

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

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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)

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

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

[Publications] 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)

[Publications] 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)

奈良坂紘一東京大学, 大学院・理学系研究科, 教授 (50016151)

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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)

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

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

[Publications] 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)

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

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

[Publications] 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)

[Publications] 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)

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

[Publications] 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)

[Publications] 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)

[Publications] 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)

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

[Publications] 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)

[Publications] 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)

[Publications] 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)

[Publications] 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)

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

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

[Publications] 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)

[Publications] 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)