1996 Fiscal Year Annual Research Report

高次構造構築法の開発

Research Project

Project/Area Number	08245101
Research Category	Grant-in-Aid for Scientific Research on Priority Areas
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)
Keywords	分子内Diels-Alder反応 / チランダマイシンB / ヘミブレベトキシンB / 脱水縮合剤 / インドールアルカロイド / キノリン / 不斉ニトロオレフィン化反応
Research Abstract	本研究では,高い生理活性や特異的な構造で注目を集めている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骨格の構築,あるいはその立体化学の制御を可能にする新しい高効率的な合成反応の開発,及び必要量の物質供給を可能にする新しい実践的合成反応の開発を目的としている。本年度の成果は以下の通りである。1)分子内Diels-Alder反応を利用する立体選択的な環形成反応を開発し,これを利用してカルビストリンAの最初の全合成を達成しその絶対構造を明らかにした。2)γ,δ-エポキシアクリレートとトリメチルアルミニウムを用いる高ジアステレオ選択的メチル化反応を開発し,チランダマイシンB及びストレプトバリシン類の合成を行った。3)アリルスズの分子内環化反応を利用し高効率的なヘテロ環化合物の立体選択的な合成を行った。これを利用し,ヘミブレベトキシンBの高効率的合成に成功した。4)塩基部位のアミノ基とリン酸基の保護基を全く必要としない脱水縮合剤を開発し,実践的なDNAの新化学合成法を確立した。5)芳香族スルフィニル化合物のPummerer反応による酸素官能基への変換反応を開発し,多環式キノン系抗腫瘍性天然物の合成を行った。6)不斉ニトロオレフィン化反応を鍵工程とするインドールアルカロイドの合成法を確立し,エゼルメトールの簡便な合成を達成した。7)金属酸化剤あるいは光増感剤を利用する新しい反応活性種の生成法を開発し,効率的な炭素骨格形成法を確立した。またオキシム化合物を利用する新しいアミノ化反応と,これを利用したキノリン類の簡便な合成法の開発を行った。

Research Products

(18 results)

All Other

All Publications (18 results)

[Publications] Y.Kohno: "Synthesis of (±)-Stemonamide by the Application of Oxidative Coupling Reactions of Stamyl Compounds with Silyl Enol Ethers." Bull.Chem.Soc.Jpn.69. 2063-2070 (1996)
[Publications] K.Uchiyama: "Synthesis of 8-Hydroxyqinolines by the Cyclization of m-Hydroxyphenethyl Ketone 0-2,4-Dinitrophenyloximes." Synlett. (印刷中). (1997)
[Publications] H.Tsutsui: "Preparation of Primary Amines by the Copper(1)Catalyzed Renction of 4,4′-Bis(trifluoromethyl)benzophenone O-Methylsufomloxime and Alkyl Grignard Reagents." Chemistry Letters. (印刷中). (1997)
[Publications] Y.Kita: "Novel and Efficient Synthesis of Sulfur-containing Heterocycles using Hypervalent lodine(III)Reagent." J.Chem.Soc.Chem.Commun. 2225-2226 (1996)
[Publications] Y.Kita: "Asymmetric Synthesis of Chiral Spirocyclanes:A New Route to the Optically Active Spiro[cyclopentane-1,1′-indan]-2,5-dione System." Tetrahedron Lett.37. 1817-1820 (1996)
[Publications] Y.Kita: "Hyperavalent lodine(III)Induced Intramolecular Cyclization of substituted Phenol Ethers bearing an Alkyl Azide Sidechain-A Novel synthesis of Quinone Imine Ketals." J.Chem.Soc.Chem.Commun.1491-1492 (1996)
[Publications] S.Kawahara: "1:1 and 1:2 Complexes of Bu_4NF and BF_3Et_2O:New Reagents for Rapid Cleavage of Silyl Ethers." Tetrahedron.Lett.37. 509-512 (1996)
[Publications] K.Seio: "Chemical Synthesis and Conformational Properties of a New Cyclouridylic acid Having an Ethylene Bridge between the Uracil 5-Position and 5′-Phosphate Group." J.Org.Chem.61. 1500-1504 (1996)
[Publications] M.Sekine: "The Chemical Synthesis of 5′-Terminal TMG-Capped Triribonucleotide m_3^<2.2.7.>G^5pppAmpUmpA of Ul RMA." J.Org.Chem.61. 4412-4422 (1996)
[Publications] K.Tatsuta: "Total synthesis of deacetyl-caloporoside,a novel inhibitor of the GABAA receptor ion channel." Tetrahedron Lett.37. 2453-2456 (1996)
[Publications] K.Tatsuta: "Total synthesis and chemical dasign of useful glycosidase inhibitors." Pure & Appl.Chem.68. 1341-1346 (1996)
[Publications] K.Tatsuta: "Synthesis and Biological Evaluation of Caloporoside Analogs." J.Antibiot.49. 713-715 (1996)
[Publications] T.Shiratani: "A Stereocontrolled Enantiospecific Route to Tirandamycin B." J.Chem.Soc.Chem.Commun.21-22 (1996)
[Publications] M.Miyashita: "Tandem Synthesis of Polypropionate Chains-Highly Stereoseiective Synthesis of Ansa Chain of Streptovaricin U and Protostreptovaricins Besed on Stereospecific Methylation of γ,δ-Epoxy Acrylates by Trimethylaluminnm." J.Chem.Soc.Chem.Commmun.1027-1028 (1996)
[Publications] 宮下正昭: "ジョロウグモ(Nephila clavata)の毒素Nephilatoxin類の合成研究" 有機合成化学協会誌. 54-10. 846-858 (1996)
[Publications] I.Kadota: "Novel Route to the Synthesis of Hdroxylated Piperdine and Pyrrolidine Derivatives via the Intramolecular Reaction of γ-Aminoallylstannane with Aldehyde." Tetrahedron Lett.37. 2109-2112 (1996)
[Publications] I.Kadota: "Intramolecular Reaction of γ-Alkoxyallylstannane with Hydrazone:Stereoselective Synthesis of β-Aminoterahydropyran and -furan." J.Chem.Soc.Chem.Commun.841-842 (1996)
[Publications] I.Kadota: "Intramolecular Reaction of Oxo-Substituted Allenyl-and Propargylstannane with Aldehyde." Tetrahedron Lett.37. 3059-3062 (1996)

1996 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] Y.Kohno: "Synthesis of (±)-Stemonamide by the Application of Oxidative Coupling Reactions of Stamyl Compounds with Silyl Enol Ethers." Bull.Chem.Soc.Jpn.69. 2063-2070 (1996)

[Publications] K.Uchiyama: "Synthesis of 8-Hydroxyqinolines by the Cyclization of m-Hydroxyphenethyl Ketone 0-2,4-Dinitrophenyloximes." Synlett. (印刷中). (1997)

[Publications] H.Tsutsui: "Preparation of Primary Amines by the Copper(1)Catalyzed Renction of 4,4′-Bis(trifluoromethyl)benzophenone O-Methylsufomloxime and Alkyl Grignard Reagents." Chemistry Letters. (印刷中). (1997)

[Publications] Y.Kita: "Novel and Efficient Synthesis of Sulfur-containing Heterocycles using Hypervalent lodine(III)Reagent." J.Chem.Soc.Chem.Commun. 2225-2226 (1996)

[Publications] Y.Kita: "Asymmetric Synthesis of Chiral Spirocyclanes:A New Route to the Optically Active Spiro[cyclopentane-1,1′-indan]-2,5-dione System." Tetrahedron Lett.37. 1817-1820 (1996)

[Publications] Y.Kita: "Hyperavalent lodine(III)Induced Intramolecular Cyclization of substituted Phenol Ethers bearing an Alkyl Azide Sidechain-A Novel synthesis of Quinone Imine Ketals." J.Chem.Soc.Chem.Commun.1491-1492 (1996)

[Publications] S.Kawahara: "1:1 and 1:2 Complexes of Bu_4NF and BF_3Et_2O:New Reagents for Rapid Cleavage of Silyl Ethers." Tetrahedron.Lett.37. 509-512 (1996)

[Publications] K.Seio: "Chemical Synthesis and Conformational Properties of a New Cyclouridylic acid Having an Ethylene Bridge between the Uracil 5-Position and 5′-Phosphate Group." J.Org.Chem.61. 1500-1504 (1996)

[Publications] M.Sekine: "The Chemical Synthesis of 5′-Terminal TMG-Capped Triribonucleotide m_3^<2.2.7.>G^5pppAmpUmpA of Ul RMA." J.Org.Chem.61. 4412-4422 (1996)

[Publications] K.Tatsuta: "Total synthesis of deacetyl-caloporoside,a novel inhibitor of the GABAA receptor ion channel." Tetrahedron Lett.37. 2453-2456 (1996)

[Publications] K.Tatsuta: "Total synthesis and chemical dasign of useful glycosidase inhibitors." Pure & Appl.Chem.68. 1341-1346 (1996)

[Publications] K.Tatsuta: "Synthesis and Biological Evaluation of Caloporoside Analogs." J.Antibiot.49. 713-715 (1996)

[Publications] T.Shiratani: "A Stereocontrolled Enantiospecific Route to Tirandamycin B." J.Chem.Soc.Chem.Commun.21-22 (1996)

[Publications] M.Miyashita: "Tandem Synthesis of Polypropionate Chains-Highly Stereoseiective Synthesis of Ansa Chain of Streptovaricin U and Protostreptovaricins Besed on Stereospecific Methylation of γ,δ-Epoxy Acrylates by Trimethylaluminnm." J.Chem.Soc.Chem.Commmun.1027-1028 (1996)

[Publications] 宮下正昭: "ジョロウグモ(Nephila clavata)の毒素Nephilatoxin類の合成研究" 有機合成化学協会誌. 54-10. 846-858 (1996)

[Publications] I.Kadota: "Novel Route to the Synthesis of Hdroxylated Piperdine and Pyrrolidine Derivatives via the Intramolecular Reaction of γ-Aminoallylstannane with Aldehyde." Tetrahedron Lett.37. 2109-2112 (1996)

[Publications] I.Kadota: "Intramolecular Reaction of γ-Alkoxyallylstannane with Hydrazone:Stereoselective Synthesis of β-Aminoterahydropyran and -furan." J.Chem.Soc.Chem.Commun.841-842 (1996)

[Publications] I.Kadota: "Intramolecular Reaction of Oxo-Substituted Allenyl-and Propargylstannane with Aldehyde." Tetrahedron Lett.37. 3059-3062 (1996)

奈良坂紘一東京大学, 大学院・理学系研究科, 教授 (50016151)