1989 Fiscal Year Annual Research Report

天然有機化合物の生体内生成機構および類似の合成反応の研究

Research Project

Project/Area Number	62303005
Research Institution	Osaka City University
Principal Investigator	林雄二大阪市立大学, 理学部, 教授 (40046917)
Co-Investigator(Kenkyū-buntansha)	村井章夫北海道大学, 理学部, 教授 (20000838) 野老山喬大阪市立大学, 理学部, 教授 (90046938) 菅隆幸広島大学, 理学部, 教授 (00033811) 後藤俊夫名古屋大学, 農学部, 教授 (20023369) 磯江幸彦大阪市立大学, 理学部, 教授 (90046946)
Keywords	イリドイド合成 / 発癌プロモ-タ- / インドラクタム / 環状モノテルペノイド生合成 / リナリル・カチオン / クレロダンジテルペンの合成 / アファナモ-ルの合成 / ファトアレキシンの内因性エリシタ-
Research Abstract	天然産イリドイドモノテルペンの一種ゲニピンを原料として、興味ある生理活性を示す多官能性イリドイド、プルメリシンやセコイリドイド、ゲンチオピクロシドなどの合成をおこなった(磯江)。皮膚刺戟性があり、発癌プロモ-タ-として注目されているテレオキシジン類の全合成をおこなってきたが、本年度は、インド-ル環に直接置換基を導入する新しい方法でインドラクVの全合成をおこなった(後藤)。環状モノテルペノイドが生合成される際のゲラニルニリン酸の環化過程において、マグネシウム(II)イオンが重要な役割を担っていることを明らかにすると共に、この過程でアリルカチオンが発生していることを^<13>C-NMR法により観測することに成功した(菅)。 2-(6'-シリル-4'-ヘキセニル)-3'4'-ジメチル-2-シクロヘキセノンの2'位に、かさ高い置換基(たとえばシリル或はアルコキシカルボニル基)をもつ基質の立体選択的環化による、8,9-ジメチル基をもつクレロダン骨格の合成を検討した(野老山)。センダン料植物のセスキテルペンアルコ-ル、アファナモ-ルのヒドロアズレン骨格は、ゲルマクラン形10員環前駆体から、ブルボナン形の中間体を経て生合成されるとの仮説に基き、適当な酸素官能基をもつブルボナン誘導体を分子内光環化により合成し、そのシクロブタン環部の選択的開裂によるアファナモ-ルAの合成を検討した(林)。植物組織の過酸化水素処理によるファトアレキシン生成の誘導は、はじめジャガイモ塊茎組織で見出したが、サツマイモ、インゲン、サトウダイコンでも同様に見出されることがわかった。そこで、ジャガイモを用いて、過酸化水素により増大するファトアレキシンの内因性エリシタ-の実在をはじめて明らかにし、その単離研究をおこなた(村井)。

Research Products

(18 results)

All Other

All Publications (18 results)

[Publications] J.Yoshida: "Methoxy(trimethylsilyl)methane and Methoxybis(trimethyl-silyl)methanes as New Reagents for Homologation." Tetrahedron Letters. 30. 219-222 (1989)
[Publications] J.Yoshida: "Formal[2+2+2]Cycloaddition of Molecular Oxygen,1,3-Diketone and Olefin.Synthesis and Reactions of Cyclic Peroxides." J.Org.Chem.54. 3383-3389 (1989)
[Publications] J.Yoshida: "Electrochemical Oxidation of Acylsilanes." Tetrahedron Letters. 30. 5293-5296 (1989)
[Publications] J.Yoshida: "Oxygenation of Alkenylsilanes in the Presence of Thio-phenol.Direct and Regiospecific Conversion of α-Phenylthiocarbonyl Compounds." J.Org.Chem.54. 5655-5657 (1989)
[Publications] S.Katsumura: "Stereoselective Synthesis of 2-Substituted 1-Methoxy-l,3-Dienes by 1,4-Elimination with Tributylstannyl-lithium." Tetrahedron Letters. 31. (1990)
[Publications] Shin-ichi Nakatsuka: "Introduction of a Hydroxyl Group onto 5-and 60Position of Indole Nucleus by Friedel Crafts' Acylation and Subsequent Baeyer-Villiger Oxidation." Heterocycles. 26. 1471-1474 (1987)
[Publications] Toshiya Masuda: "Efficient Synthesis and Chemistry of Indolactam-V and Its Analogues." Age.Biol.Chem.53. 2257-2260 (1989)
[Publications] T.Suga: "Facile and Stereospecific Synthesis of(s)-and-(R)-[2-^2H]Isopentenyl Phyrophosphate." J.Chem.Soc.,Perkin Trans.1. 2845-2848 (1987)
[Publications] T.Suga: "Biosynthesis of Cyclic Monoterpenoids.Involement of Stereochemically Specified Linalyl Cation in the Cyclization of C_<10>-Prenyl Chain." Chemistry Letters. 115-118 (1988)
[Publications] T.Yamamitsu: "Synthesis of 4-and 5-Regioselectively Deuterated Geranyl Diphosphates." J.Chem.Soc.,Perkin Trans.1. 1811-1814 (1989)
[Publications] T.Tokoroyama: "Folding Strain Control for Remote Stereocontrol:Dia-stereoselectivity in the Ring Closure Reactions of 2-(6'-Trimethylsilylhex-4'-enyl)cyclohex-2-enones with Alkyl Groups at Various Positions in the Side Chain." J.Chem.Soc.,Chem.Commun.1572-1573 (1989)
[Publications] K.Asao: "Stereoselective cyclization of(E)-and(Z)0Dimethyl-8-trimethylsilyl-6-octanals." Tetrahedron Letters. 30. 6397- (1989)
[Publications] M.Nishizawa: "Dukunolide D,E and F:New Tetranortriterpenoids from Seeds of lansium domesticum." Phytochemistry. 27. 237-239 (1988)
[Publications] M.Nishizawa: "Isolation of a New Cycloartanoid Triterpene from Leaves of lansium domesticum,Novel Skin-Tuor Promotion Inhibitors." Tetrahrdron Letters. 30. 5615-5618 (1989)
[Publications] Chairul: "Malonate Half-esters of Homolanostanoid from an Asian Ganoderma Fungus." Phytochemistry. 29. (1990)
[Publications] A.Murai: "An Efficient Synthesis of 15-Oxygenated T-types Spiro-vetivanes:Its Application to the Synthesis of(+)-[8,8-^2H_2]Isolubimin." Chemistry Letters. 651-654 (1987)
[Publications] A.Murai: "Biosynthesis of Phytoberin." Chemistry Letters. 1377-1378 (1987)
[Publications] A.Murai: "Phytoalexin Chemistry and Action,in“Pesticide Science and Biotechnology"ed.by R.Greenhalgh & T.R.Roberts" Blackwell Scientific Publ., 81-88 (1987)

1989 Fiscal Year Annual Research Report

天然有機化合物の生体内生成機構および類似の合成反応の研究

Principal Investigator

林 雄二 大阪市立大学, 理学部, 教授 (40046917)

Research Products

[Publications] J.Yoshida: "Methoxy(trimethylsilyl)methane and Methoxybis(trimethyl-silyl)methanes as New Reagents for Homologation." Tetrahedron Letters. 30. 219-222 (1989)

[Publications] J.Yoshida: "Formal[2+2+2]Cycloaddition of Molecular Oxygen,1,3-Diketone and Olefin.Synthesis and Reactions of Cyclic Peroxides." J.Org.Chem.54. 3383-3389 (1989)

[Publications] J.Yoshida: "Electrochemical Oxidation of Acylsilanes." Tetrahedron Letters. 30. 5293-5296 (1989)

[Publications] J.Yoshida: "Oxygenation of Alkenylsilanes in the Presence of Thio-phenol.Direct and Regiospecific Conversion of α-Phenylthiocarbonyl Compounds." J.Org.Chem.54. 5655-5657 (1989)

[Publications] S.Katsumura: "Stereoselective Synthesis of 2-Substituted 1-Methoxy-l,3-Dienes by 1,4-Elimination with Tributylstannyl-lithium." Tetrahedron Letters. 31. (1990)

[Publications] Shin-ichi Nakatsuka: "Introduction of a Hydroxyl Group onto 5-and 60Position of Indole Nucleus by Friedel Crafts' Acylation and Subsequent Baeyer-Villiger Oxidation." Heterocycles. 26. 1471-1474 (1987)

[Publications] Toshiya Masuda: "Efficient Synthesis and Chemistry of Indolactam-V and Its Analogues." Age.Biol.Chem.53. 2257-2260 (1989)

[Publications] T.Suga: "Facile and Stereospecific Synthesis of(s)-and-(R)-[2-^2H]Isopentenyl Phyrophosphate." J.Chem.Soc.,Perkin Trans.1. 2845-2848 (1987)

[Publications] T.Suga: "Biosynthesis of Cyclic Monoterpenoids.Involement of Stereochemically Specified Linalyl Cation in the Cyclization of C_<10>-Prenyl Chain." Chemistry Letters. 115-118 (1988)

[Publications] T.Yamamitsu: "Synthesis of 4-and 5-Regioselectively Deuterated Geranyl Diphosphates." J.Chem.Soc.,Perkin Trans.1. 1811-1814 (1989)

[Publications] T.Tokoroyama: "Folding Strain Control for Remote Stereocontrol:Dia-stereoselectivity in the Ring Closure Reactions of 2-(6'-Trimethylsilylhex-4'-enyl)cyclohex-2-enones with Alkyl Groups at Various Positions in the Side Chain." J.Chem.Soc.,Chem.Commun.1572-1573 (1989)

[Publications] K.Asao: "Stereoselective cyclization of(E)-and(Z)0Dimethyl-8-trimethylsilyl-6-octanals." Tetrahedron Letters. 30. 6397- (1989)

[Publications] M.Nishizawa: "Dukunolide D,E and F:New Tetranortriterpenoids from Seeds of lansium domesticum." Phytochemistry. 27. 237-239 (1988)

[Publications] M.Nishizawa: "Isolation of a New Cycloartanoid Triterpene from Leaves of lansium domesticum,Novel Skin-Tuor Promotion Inhibitors." Tetrahrdron Letters. 30. 5615-5618 (1989)

[Publications] Chairul: "Malonate Half-esters of Homolanostanoid from an Asian Ganoderma Fungus." Phytochemistry. 29. (1990)

[Publications] A.Murai: "An Efficient Synthesis of 15-Oxygenated T-types Spiro-vetivanes:Its Application to the Synthesis of(+)-[8,8-^2H_2]Isolubimin." Chemistry Letters. 651-654 (1987)

[Publications] A.Murai: "Biosynthesis of Phytoberin." Chemistry Letters. 1377-1378 (1987)

[Publications] A.Murai: "Phytoalexin Chemistry and Action,in“Pesticide Science and Biotechnology"ed.by R.Greenhalgh & T.R.Roberts" Blackwell Scientific Publ., 81-88 (1987)

林雄二大阪市立大学, 理学部, 教授 (40046917)