1989 年度実績報告書

天然生体作用物質に関する多角的研究

研究課題

研究課題/領域番号	01303003
研究機関	東北大学
研究代表者	宇田尚東北大学, 非水溶液化学研究所, 教授 (40006292)
研究分担者	野老山喬大阪市立大学, 理学部, 教授 (90046938) 山田静之名古屋大学, 理学部, 教授 (90022540) 柿沢寛筑波大学, 化学系, 教授 (50015492) 平間正博東北大学, 理学部, 教授 (30165203) 白浜晴久北海道大学, 理学部, 教授 (00000802)
キーワード	生体作用物質 / テルペノイド / アルカロイド / イリドイド / ステロイド / 全合成 / 構造決定
研究概要	1.生体作用物質の単離・構造と生体内生成:沖縄産軟サンゴなどに含まれる抗菌性や細胞毒性を示すテルペノイド類(柿沢)、一種の海洋無脊椎動物中の致死作用性をもつセコステロイド類(越智)、伊豆産海綿中の有毒性テルペン系アルカロイド(上村)、ベッコウバチ毒液中の神経抑制作用物質(奥村)、インドネシア産サルノコシカケ科きのこ中の抗腫瘍プロモ-タ活性を有するホモラノスタノイド類(林)、および放線菌中の植物成長抑制物質(中山)を単離しそれらの構造を決定した。また、マサキ成熟果実よりセスキテルペンの単離(森)および稲モミガラの水溶性区分中での自己発芽抑制物質の存在の確認(加藤)を行い、現在構造決定や単離を解討中である。またオオワライタケの毒成分の立体構造決定のための部分合成(白浜)を行った。さらに、ラクトペルオキシダ-ゼによるロ-レンジオ-ルの閉環過程(村井)やゲラニルニリン酸とマグネシウムイオンとの配位(菅)を明らかにした。 2.生体作用物質の合成法、合成と作用機作:種々の生物活性テルペノイドの合成のため中間体としてゲルマクラン型10員環状化合物(露木)、や光学活性な4-置換-1-デカロン類(宇田)、多置換3-シクロヘキセノ-ル類(野老山)、およびエポキシイソプレノイド類(児玉)などを、また光学活性ピログルタミン酸よりアルカロイド合成中間体(吉越)を合成した。また免疫活性糖脂質(楠本)や抗生物質(山村)の活性部位の部分構造の合成やアルカロイド活性種によるヌクレオシド類の化学修飾(山田)も行った。天然物自身としては、3種類のイリドイド類のアグリコン部(磯江)とキノコ発光体ランプテロフラビン(磯部)の合成を達成した。さらにネオカルチノスタチンの環状および非環状モデルを合成し、新しい活性化機構を示すことを見出した(平間)。以上の結果をふまえ、全合成を推進し、かつ活性作用機構を検討する。

研究成果

(30件)

すべてその他

すべて文献書誌 (30件)

[文献書誌] Hisahiro Hagiwara: "A Synthesis of (±)-Khusilal" Chem.Lett.2067-2068 (1989)
[文献書誌] Hisahiro Hagiwara: "Asymmetric Two-fold Michael Reaction.Synthesis of Optically Active 4-Substituted 1-Decalones from Trimethylsilyl Enol Ether of 1-Acetylcyclohexene" Chem.Lett.2149-2152 (1989)
[文献書誌] Akio Fukuzawa: "Laureoxolane, a New Bromo Ether form Laurencia nipponica" Tetrahedron Lett.30. 3665-3668 (1989)
[文献書誌] Akio fukuzaw: "A Sesquiterpene Alcohol from the Red Alga Laurencia nipponica Yamada" Phytochemistry印刷中.
[文献書誌] Masaru Hashimoto: "The Absolute Configuration of 4,6-Decadiyn-1,3,8-triol Isolated from Gymmopilus spectabilis" Bull.Chem.Soc.Jpn.62. 2751-2752 (1989)
[文献書誌] Fukushi Hiroyama: "4-Aminopyridine-2,3-dicarboxylic Acid from Citocybe acromelalga" Phytochemistry. 28. 1133-1135 (1989)
[文献書誌] Masahiro Hirama: "The 10-Membered Ring Analogues of Neocarzinostatin Chromophore:Design,Synthesis, and Mode of Decomposition" J.Am.Chem.Soc.111. 4120-4122 (1989)
[文献書誌] Masahiro Hirama: "Radical Triggering Mechanism for Aromatization of Neocarzinostatin Chromophoe:Important Rout in aerobic" 発表予定.
[文献書誌] Michiharu Kato: "Stereoselective Synthesis of Natural trans-Phyrrolidines from PyrogIutamic Acid" 発表予定.
[文献書誌] G.C.Zheng: "Cytotoxic Hydroxyperoxy-trans-bicyclogermacrenes from the Actiniaria Anthopleura pacifica Uchida" J.Org.Chem.印刷中.
[文献書誌] Shigeru Nishiyama: "Biomimetic Synthesis and Stereostructure of K-13,a Novel Inhibitor of Angiotensin I Converting Enzyme" Tetrahedron Lett.30. 379-382 (1989)
[文献書誌] Yoshikazu Suzuki: "Synthetic Study on Vancomycin:Synthesis of a Macrocyclic Tetrapeptide as a Plausible Active Center in Vancomycin" Tetrahderon Lett.30. 6043-6046 (1989)
[文献書誌] Kazuyoshi Ohashi: "The Constituents of the Venom of Cyphononyx dorsalis" 発表予定.
[文献書誌] Hideaki Karaki: "Inhibitory Effect of a Toxin Okadaic Acid,Isolated from the Black Sponge on Smooth Muscle and Platelets" Br.J.Pharmacol.98. 590-596 (1989)
[文献書誌] Duangchan Uyakul: "Lampteromyces Bioluminescence---3.Structure of Lampteroflavin,the Light Emitter in the Luminous Mushroom,L.japonicus" Bioorg.Chem.17. 454-460 (1989)
[文献書誌] Miniru Isobe: "Lampteromyces Bioluminescence---5.Chemical Synthesis of Lamptereflavin as Mushroom Light Emitter" Tetrahedron Lett.31. 717-718 (1990)
[文献書誌] Koichi Fukase: "4-Nitrobenzyl Group for Protection of Hydroxy Functions" Tetrahedron Lett.31. 389-392 (1990)
[文献書誌] Mugio Nishizawa: "Isolation of a New Cycloartanoid Triterpene from Leaves of Lansium domesticum,Novel Skin-tumor Promotion Inhibitors" Tetrahedron lett.30. 5615-5618 (1989)
[文献書誌] Chairul: "Malonate Half-esters of Homolanostanoid from Asian Ganoderma Fungus" Phytochemistry.
[文献書誌] Hideo Iio: "Synthesis of cis- and trans-15,16-Epoxycleroda-13(16),14-dien-3-ones:Incompatibility with the Structure of Cascarillone" J.Chem.Soc.,Perkin Trans.1. 1359-1360 (1989)
[文献書誌] Hideo Iio: "Cascarillone:Revised Structure and Total Synthesis" J.Chem.Soc.,Perkin Trans.1. 1360-1361 (1989)
[文献書誌] Shinya Fujiwara: "Stereoselective Synthesis of 2-Substituted 1-Methoxy-1,3-Dienes by 1,4-Elimination with Tributylstannyllithium" Tetrahedron Lett.
[文献書誌] Sachihiko Isoe: "synthesis of Allamandicin,Plumericin and Plumieride Aglycone from(+)-Genipin" 発表予定.
[文献書誌] Akira Hirota: "Structure of Kaimonolide A,a Novel Macrolide Plant Growth Inhibitor from a Streptomyces Strain" Agric.Biol.Chem.53. 2831-2833 (1989)
[文献書誌] Takayuki Suga: "Glycinoprenols:Novel Polyprenols Possessing a Phythl Residue from the Leaves of Soybean" J.Org.Chem. 54. 3390-3393 (1989)
[文献書誌] Tohru Yamamitsu: "Synthesis of 4-and 5-Regioselectively Deuterated Geranyl Diphosphate" J.Chem.Soc.,Perkin Trans.1. 1811-1814 (1989)
[文献書誌] Masamitsu Ochi: "Acanthopherol A and B,Two Novel Secosterole with Brine Shrimp Lethalty from a Gorgonian Acanthogorgiidae sp." 発表予定.
[文献書誌] Mitsuaki Kodama: "Convenient Synthesis of ChiralEpoxyisopenoids by Yeast Reduction" Tetrahedron Lett.
[文献書誌] 磯部稔: "天然物化学の新しい展開-その考え方と進め方" 化学同人, 166 (1988)
[文献書誌] Daisuke Uemura: "Studies in Natural Products Chemistry,Vol.5(Part B)Atta-ur-Rahman,Ed." Elsevier,Amsterdam, 906 (1989)

1989 年度 実績報告書

天然生体作用物質に関する多角的研究

研究代表者

宇田 尚 東北大学, 非水溶液化学研究所, 教授 (40006292)

研究成果

[文献書誌] Hisahiro Hagiwara: "A Synthesis of (±)-Khusilal" Chem.Lett.2067-2068 (1989)

[文献書誌] Hisahiro Hagiwara: "Asymmetric Two-fold Michael Reaction.Synthesis of Optically Active 4-Substituted 1-Decalones from Trimethylsilyl Enol Ether of 1-Acetylcyclohexene" Chem.Lett.2149-2152 (1989)

[文献書誌] Akio Fukuzawa: "Laureoxolane, a New Bromo Ether form Laurencia nipponica" Tetrahedron Lett.30. 3665-3668 (1989)

[文献書誌] Akio fukuzaw: "A Sesquiterpene Alcohol from the Red Alga Laurencia nipponica Yamada" Phytochemistry印刷中.

[文献書誌] Masaru Hashimoto: "The Absolute Configuration of 4,6-Decadiyn-1,3,8-triol Isolated from Gymmopilus spectabilis" Bull.Chem.Soc.Jpn.62. 2751-2752 (1989)

[文献書誌] Fukushi Hiroyama: "4-Aminopyridine-2,3-dicarboxylic Acid from Citocybe acromelalga" Phytochemistry. 28. 1133-1135 (1989)

[文献書誌] Masahiro Hirama: "The 10-Membered Ring Analogues of Neocarzinostatin Chromophore:Design,Synthesis, and Mode of Decomposition" J.Am.Chem.Soc.111. 4120-4122 (1989)

[文献書誌] Masahiro Hirama: "Radical Triggering Mechanism for Aromatization of Neocarzinostatin Chromophoe:Important Rout in aerobic" 発表予定.

[文献書誌] Michiharu Kato: "Stereoselective Synthesis of Natural trans-Phyrrolidines from PyrogIutamic Acid" 発表予定.

[文献書誌] G.C.Zheng: "Cytotoxic Hydroxyperoxy-trans-bicyclogermacrenes from the Actiniaria Anthopleura pacifica Uchida" J.Org.Chem.印刷中.

[文献書誌] Shigeru Nishiyama: "Biomimetic Synthesis and Stereostructure of K-13,a Novel Inhibitor of Angiotensin I Converting Enzyme" Tetrahedron Lett.30. 379-382 (1989)

[文献書誌] Yoshikazu Suzuki: "Synthetic Study on Vancomycin:Synthesis of a Macrocyclic Tetrapeptide as a Plausible Active Center in Vancomycin" Tetrahderon Lett.30. 6043-6046 (1989)

[文献書誌] Kazuyoshi Ohashi: "The Constituents of the Venom of Cyphononyx dorsalis" 発表予定.

[文献書誌] Hideaki Karaki: "Inhibitory Effect of a Toxin Okadaic Acid,Isolated from the Black Sponge on Smooth Muscle and Platelets" Br.J.Pharmacol.98. 590-596 (1989)

[文献書誌] Duangchan Uyakul: "Lampteromyces Bioluminescence---3.Structure of Lampteroflavin,the Light Emitter in the Luminous Mushroom,L.japonicus" Bioorg.Chem.17. 454-460 (1989)

[文献書誌] Miniru Isobe: "Lampteromyces Bioluminescence---5.Chemical Synthesis of Lamptereflavin as Mushroom Light Emitter" Tetrahedron Lett.31. 717-718 (1990)

[文献書誌] Koichi Fukase: "4-Nitrobenzyl Group for Protection of Hydroxy Functions" Tetrahedron Lett.31. 389-392 (1990)

[文献書誌] Mugio Nishizawa: "Isolation of a New Cycloartanoid Triterpene from Leaves of Lansium domesticum,Novel Skin-tumor Promotion Inhibitors" Tetrahedron lett.30. 5615-5618 (1989)

[文献書誌] Chairul: "Malonate Half-esters of Homolanostanoid from Asian Ganoderma Fungus" Phytochemistry.

[文献書誌] Hideo Iio: "Synthesis of cis- and trans-15,16-Epoxycleroda-13(16),14-dien-3-ones:Incompatibility with the Structure of Cascarillone" J.Chem.Soc.,Perkin Trans.1. 1359-1360 (1989)

[文献書誌] Hideo Iio: "Cascarillone:Revised Structure and Total Synthesis" J.Chem.Soc.,Perkin Trans.1. 1360-1361 (1989)

[文献書誌] Shinya Fujiwara: "Stereoselective Synthesis of 2-Substituted 1-Methoxy-1,3-Dienes by 1,4-Elimination with Tributylstannyllithium" Tetrahedron Lett.

[文献書誌] Sachihiko Isoe: "synthesis of Allamandicin,Plumericin and Plumieride Aglycone from(+)-Genipin" 発表予定.

[文献書誌] Akira Hirota: "Structure of Kaimonolide A,a Novel Macrolide Plant Growth Inhibitor from a Streptomyces Strain" Agric.Biol.Chem.53. 2831-2833 (1989)

[文献書誌] Takayuki Suga: "Glycinoprenols:Novel Polyprenols Possessing a Phythl Residue from the Leaves of Soybean" J.Org.Chem. 54. 3390-3393 (1989)

[文献書誌] Tohru Yamamitsu: "Synthesis of 4-and 5-Regioselectively Deuterated Geranyl Diphosphate" J.Chem.Soc.,Perkin Trans.1. 1811-1814 (1989)

[文献書誌] Masamitsu Ochi: "Acanthopherol A and B,Two Novel Secosterole with Brine Shrimp Lethalty from a Gorgonian Acanthogorgiidae sp." 発表予定.

[文献書誌] Mitsuaki Kodama: "Convenient Synthesis of ChiralEpoxyisopenoids by Yeast Reduction" Tetrahedron Lett.

[文献書誌] 磯部稔: "天然物化学の新しい展開-その考え方と進め方" 化学同人, 166 (1988)

[文献書誌] Daisuke Uemura: "Studies in Natural Products Chemistry,Vol.5(Part B)Atta-ur-Rahman,Ed." Elsevier,Amsterdam, 906 (1989)

1989 年度実績報告書

宇田尚東北大学, 非水溶液化学研究所, 教授 (40006292)