1990 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) 柿澤寛筑波大学, 化学系, 教授 (50015492) 平間正博東北大学, 理学部, 教授 (30165203) 白濱晴久北海道大学, 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 / ペプチド / 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:沖縄産軟サンゴに含まれる細胞毒性ビスセンブラノイド(柿澤)、海産無脊椎動物中の昆虫成長阻害活性を示すジテルペノイド(越智)、海綿に含まれる抗炎症性アルカロイドおよび渦鞭毛藻の有毒性大分子ポリエ-テル(上村)、ベッコウバチ毒液中の神経活性ペプチド(奥村)、きのこドクササゴ中の生理活性アミノ酸(白濱)、熱帯産サルノコシカケ科きのこ中の抗腫瘍活性ラノスタノイド類(林)、および、或る種のかび中の抗菌活性物質(中山)を単離しそれらの構造を決定ないし推定した。また、マサキ果実よりセスキテルペン(森)およびモミガラ中の生長調節物質(加藤)を単離し、現在構造決定を検討中である。さらに、ロ-レンジオ-ルの海藻由来のブロモパ-オキシダ-ゼによる含エ-テル他天然物への閉環(村井)やゲラニル二リン酸の位置選択的水素脱離(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合成のための重要中間体の合成(高橋、児玉)や鍵反応の立体選択性(野老山)を検討した。また、テトロドトキシン合成の重要中間体(磯部)、バンコマイシン活性部位のヘキサペプチド(山村)、およびグラム陽性菌のリポタイコ酸の糖脂質部(楠本)を合成した。天然物自身としては、発癌プロモ-タ活性サキュラタ-ルを含め、種々の生体活性を示すテルペノイド約10種の不斉合成(宇田)やイリドイド、ジエニピンの昆虫誘引性2種を含め4種のイリドイド類への変換(磯江)を達成した。また、発癌性ピロリチジンアルカロイドのアルキル化反応の特性(山田)や共役インエンクレムレンの合成とその芳香族化様式(平間)を明らかにした。以上、種々の生体作用物質に関する今後の研究について多くの示唆を得た。

研究成果

(42件)

すべてその他

すべて文献書誌 (42件)

[文献書誌] Akio Fukuzawa: "A Direct Enzymatic Synthesis of Laurencin from Laurediol" Chem.Lett.1579-1580 (1990)
[文献書誌] Akio Fukuzawa: "Structure Elucidation of Laureoxanyne,A New Nonisoprenoid C_<15> Enyne,Using Lactoperoxidase" Tetrahedron Lett.31. 4895-4898 (1990)
[文献書誌] Kimiko Hashimoto: "Simple Analogs of Acromeric Acid,which are Highly Active Agonists of Kainate Type Neuroexcitant" Tetrahedron Lett.31. 7047-7050 (1990)
[文献書誌] Kimiko Hashimoto: "Synthesis of New Acromeric Congeners:Novel Neuroーexcitatory Amino Acids Acting on Glutamate Receptor" Tetrahedron Lett.
[文献書誌] Toshiyuki Tanaka: "Oxidative Triggering for Aromatization of the Neoーcarzinostatin Chromophore" Tetrahedron Lett.31. 5947-5950 (1990)
[文献書誌] Kenshu Fujiwara: "Enyne 3 cumulene.Synthesis and Mode of Aromatization" J.Org.Chem.
[文献書誌] Nobuyuki Harada: "Efficient Preparation of Optically Pure WielandーMiescher Ketone and Confirmation of Its Absolute Stereochemistry by the CD Exciton Chirality Method" Synthesis. 53-56 (1990)
[文献書誌] Nobuyuki Harada: "Total Synthesis and Absolute Stereochemistry of (+)ーXestoquinone and Xestoquinol" J.Org.Chem.55. 3158-3163 (1990)
[文献書誌] Hisahiro Hagiwara: "Total Synthesis of (+)ーPerrottetianal A" J.Chem.Soc.,Perkin Trans.l. 1901-1908 (1990)
[文献書誌] Hisahiro Hagiwara: "Oneーpot Annulation to Tricyclo[5.3.1.0^<3,6>]undecanー2,6ーdiones by Sequential Three Fold Michael Reactions.A Formal Synthesis of (±)ーSeychellene" J.Chem.Soc.,Perkin Trans.l. 2109-2113 (1990)
[文献書誌] Hisahiro Hagiwara: "Total Synthesis and Absolute Stereostructure of (+)ーDysideapalaunic Acid" J.Org.Chem.
[文献書誌] Hiroshi Kosugi: "Total Synthesis of (+)ーMesembrine and (+)ーTrichodiene" 発表予定.
[文献書誌] Hiroshi Kosugi: "Total Synthesis of transー(ー)ーTetrahydroactinidiolide,(+)ーDihydroactinidiolide,and (ー)ーNorambreinolide" 発表予定.
[文献書誌] Takenori Kusumi: "A Novel Chlorinated Biscembranoid from the Marine Soft Coral <Sarcophyton>___ー <glaucum>___ー" J.Org.Chem.55. 6286-6289 (1990)
[文献書誌] Midori O.Ishitsuka: "Methyl Sarcoate,a Half of the Marine Biscembranoids,from the Soft Coral <Sarcophyton>___ー <glaucum>___ー" Tetrahedron Lett.
[文献書誌] Tadahiro Kato: "Growth Regulators in Rice Husk" 発表予定.
[文献書誌] Tetsuo Furuno: "Synthetic Studies on Nineーmembered Ring Diterpenoids:Stereoselective Construction of Optically Active lーOxaspiro[2.8]undecenone Derivatives" Heterocycles. 31. 1577-1580 (1990)
[文献書誌] Yoshikazu Suzuki: "Synthetic Study on Vancomycin:Synthesis of Macrocyclic Tetrapeptide as a Plausible Active Center in Vancomycin" Tetrahedron Lett.30. 6043-6046 (1989)
[文献書誌] Yoshikazu Suzuki: "Synthesis of a Bicyclic Hexapeptide as a Plausible Active Center in Vancomycin" Tetrahedron Lett.31. 4053-4056 (1990)
[文献書誌] K.Ohashi: "The Constituents of the Venom of <Cyphononyx dorsalis>___ー" 発表予定.
[文献書誌] Daisuke Uemura: "Structure Activity Studies of the nonTPAーType Tumor Promoter Palytoxin in Swiss 3T3 Cells" Cancer Res.49. 5837-5842 (1989)
[文献書誌] Daisuke Uemura: "Cytotxic Alkaloids from the Marine Sponges" J.Nat.Prod.
[文献書誌] Haruki Niwa: "Alkylation of Nucleosides by Dehydromonocrotaline,the Putative Toxic Metabolite of the Carcinogenic Pyrroliーzidine Alkaloid Monocrotaline" Tetrahedron Lett.
[文献書誌] Minoru Isobe: "Synthetic Studies on (ー)ーTetrodotoxin(3)ーーNitrogenation through Overman Rearrangement and Guanidin Ring Formation" Tetrahedron Lett.31. 3327-3330 (1990)
[文献書誌] A.Herunsalee: "Stereoselective Synthesis directed toward Polyoxygenated Compounds,Synthesis of A KDN Equivalent" Synlett.199-200 (1990)
[文献書誌] MingーHai Wang: "Suppressive Effect of Lipid A Partial Structure on Lipopolysaccharide or Lipid Aーinduced Release of Iinterleukin l by Human Monocytes" FEMS Microbiology Immunology. 64. 179-186 (1990)
[文献書誌] Koichi Fukase: "4ーPivaloylaminobenzyl Group.a New Temporary Protection for Hydroxyl Functions" Tetrahedron Lett.
[文献書誌] Yuji Hayashi: "Malonate Halfーesters of Homolanostanoid from an Asian <Ganoderma>___ー Fungus" Phytochemistry. 29. 923-928 (1990)
[文献書誌] Yuji Hayashi: "Structure of Syzygiol:a Skinーtumor Promotion Inhibitor" Tetrahedron Lett.32. 211-212 (1991)
[文献書誌] Kazuhiko Asao: "Convenient Stereoselective Syntheses of(6E)ー and (6Z)ー 5,6ーDimethylー8ーsilylー6ーoctanols" Synthesis. 382-386 (1990)
[文献書誌] Takashi Tokoroyama: "Synthetic Studies on Terpenic Compounds.XXXIII.A Total Synthesis of (±)ー15,16ーEpoxyーcisーclerodaー3,13(16),14ーtriene" Bull.Chem.Soc.Jpn.63. 1720-1728 (1990)
[文献書誌] Sachihiko Isoe: "Synthesis of Nepetalactol and Neomatatabiol from (+)ーGenipin"
[文献書誌] Sachihiko Isoe: "Synthesis of (+)ーTecomanin from (+)ーGenipin"
[文献書誌] Eiji Kitamura: "(1R,6R,9S,10S)ー9ーChloroー10ーhydroxyー8ーmethoxycarbonylー4ーmethyleneー2,5ーdioxabicyclo[4.4.0]decー3ーoneー7ーene.A First Chlorineーcontaining Shikimateーrelated metabolite from Fungi" Tetrahedron Lett.31. 4605-4608 (1990)
[文献書誌] Yoshikazu Hiraga: "Facile Synthesis of Regioselective Deuteriated (3R)ー(ー)ー[8,8,8ー^2H_3]Linalool" Chem.Lett.49-52 (1991)
[文献書誌] Shunsuke Izumi: "Synthesis of [10,10,10ー^2H_3]Geranyl Diphosphate" J.Labelled Compd.Radiopharm.印刷中.
[文献書誌] Masamitsu Ochi: "Litophynin D and E,Two New Diterpenoids from a Soft Coral <Litophyton>___ー sp." Chem.Lett.2183-2186 (1990)
[文献書誌] Masamitsu Ochi: "Calicoferols A and B,Two Novel Secosterols Possessing BrineーShrimp Lethality from the Gorgonian <Calicogorgia>___ー sp." Chem.Lett.
[文献書誌] Mitsuaki Kodama: "Convenient Synthesis of Chiral Epoxyisoprenoids by Yeast Reduction" Tetrahedron Lett.31. 4025-4026 (1990)
[文献書誌] 白濱晴久: "生体機能解明のための化学合成(部分担当)" 化学同人, 253 (1990)
[文献書誌] Daisuke Uemura: "Bioorganic Marine Chemistry,Vol.4" Springer Verlag, 1-30 (1991)
[文献書誌] Minoru Isobe: "Ansamacrolides Recent Progress in the Chemical Synthesis of Antibiotics.Chapter 4,pp103ー134" SpringerーVerlag, 803 (1990)

1990 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] Akio Fukuzawa: "A Direct Enzymatic Synthesis of Laurencin from Laurediol" Chem.Lett.1579-1580 (1990)

[文献書誌] Akio Fukuzawa: "Structure Elucidation of Laureoxanyne,A New Nonisoprenoid C_<15> Enyne,Using Lactoperoxidase" Tetrahedron Lett.31. 4895-4898 (1990)

[文献書誌] Kimiko Hashimoto: "Simple Analogs of Acromeric Acid,which are Highly Active Agonists of Kainate Type Neuroexcitant" Tetrahedron Lett.31. 7047-7050 (1990)

[文献書誌] Kimiko Hashimoto: "Synthesis of New Acromeric Congeners:Novel Neuroーexcitatory Amino Acids Acting on Glutamate Receptor" Tetrahedron Lett.

[文献書誌] Toshiyuki Tanaka: "Oxidative Triggering for Aromatization of the Neoーcarzinostatin Chromophore" Tetrahedron Lett.31. 5947-5950 (1990)

[文献書誌] Kenshu Fujiwara: "Enyne 3 cumulene.Synthesis and Mode of Aromatization" J.Org.Chem.

[文献書誌] Nobuyuki Harada: "Efficient Preparation of Optically Pure WielandーMiescher Ketone and Confirmation of Its Absolute Stereochemistry by the CD Exciton Chirality Method" Synthesis. 53-56 (1990)

[文献書誌] Nobuyuki Harada: "Total Synthesis and Absolute Stereochemistry of (+)ーXestoquinone and Xestoquinol" J.Org.Chem.55. 3158-3163 (1990)

[文献書誌] Hisahiro Hagiwara: "Total Synthesis of (+)ーPerrottetianal A" J.Chem.Soc.,Perkin Trans.l. 1901-1908 (1990)

[文献書誌] Hisahiro Hagiwara: "Oneーpot Annulation to Tricyclo[5.3.1.0^<3,6>]undecanー2,6ーdiones by Sequential Three Fold Michael Reactions.A Formal Synthesis of (±)ーSeychellene" J.Chem.Soc.,Perkin Trans.l. 2109-2113 (1990)

[文献書誌] Hisahiro Hagiwara: "Total Synthesis and Absolute Stereostructure of (+)ーDysideapalaunic Acid" J.Org.Chem.

[文献書誌] Hiroshi Kosugi: "Total Synthesis of (+)ーMesembrine and (+)ーTrichodiene" 発表予定.

[文献書誌] Hiroshi Kosugi: "Total Synthesis of transー(ー)ーTetrahydroactinidiolide,(+)ーDihydroactinidiolide,and (ー)ーNorambreinolide" 発表予定.

[文献書誌] Takenori Kusumi: "A Novel Chlorinated Biscembranoid from the Marine Soft Coral <Sarcophyton>___ー <glaucum>___ー" J.Org.Chem.55. 6286-6289 (1990)

[文献書誌] Midori O.Ishitsuka: "Methyl Sarcoate,a Half of the Marine Biscembranoids,from the Soft Coral <Sarcophyton>___ー <glaucum>___ー" Tetrahedron Lett.

[文献書誌] Tadahiro Kato: "Growth Regulators in Rice Husk" 発表予定.

[文献書誌] Tetsuo Furuno: "Synthetic Studies on Nineーmembered Ring Diterpenoids:Stereoselective Construction of Optically Active lーOxaspiro[2.8]undecenone Derivatives" Heterocycles. 31. 1577-1580 (1990)

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

[文献書誌] Yoshikazu Suzuki: "Synthesis of a Bicyclic Hexapeptide as a Plausible Active Center in Vancomycin" Tetrahedron Lett.31. 4053-4056 (1990)

[文献書誌] K.Ohashi: "The Constituents of the Venom of <Cyphononyx dorsalis>___ー" 発表予定.

[文献書誌] Daisuke Uemura: "Structure Activity Studies of the nonTPAーType Tumor Promoter Palytoxin in Swiss 3T3 Cells" Cancer Res.49. 5837-5842 (1989)

[文献書誌] Daisuke Uemura: "Cytotxic Alkaloids from the Marine Sponges" J.Nat.Prod.

[文献書誌] Haruki Niwa: "Alkylation of Nucleosides by Dehydromonocrotaline,the Putative Toxic Metabolite of the Carcinogenic Pyrroliーzidine Alkaloid Monocrotaline" Tetrahedron Lett.

[文献書誌] Minoru Isobe: "Synthetic Studies on (ー)ーTetrodotoxin(3)ーーNitrogenation through Overman Rearrangement and Guanidin Ring Formation" Tetrahedron Lett.31. 3327-3330 (1990)

[文献書誌] A.Herunsalee: "Stereoselective Synthesis directed toward Polyoxygenated Compounds,Synthesis of A KDN Equivalent" Synlett.199-200 (1990)

[文献書誌] MingーHai Wang: "Suppressive Effect of Lipid A Partial Structure on Lipopolysaccharide or Lipid Aーinduced Release of Iinterleukin l by Human Monocytes" FEMS Microbiology Immunology. 64. 179-186 (1990)

[文献書誌] Koichi Fukase: "4ーPivaloylaminobenzyl Group.a New Temporary Protection for Hydroxyl Functions" Tetrahedron Lett.

[文献書誌] Yuji Hayashi: "Malonate Halfーesters of Homolanostanoid from an Asian <Ganoderma>___ー Fungus" Phytochemistry. 29. 923-928 (1990)

[文献書誌] Yuji Hayashi: "Structure of Syzygiol:a Skinーtumor Promotion Inhibitor" Tetrahedron Lett.32. 211-212 (1991)

[文献書誌] Kazuhiko Asao: "Convenient Stereoselective Syntheses of(6E)ー and (6Z)ー 5,6ーDimethylー8ーsilylー6ーoctanols" Synthesis. 382-386 (1990)

[文献書誌] Takashi Tokoroyama: "Synthetic Studies on Terpenic Compounds.XXXIII.A Total Synthesis of (±)ー15,16ーEpoxyーcisーclerodaー3,13(16),14ーtriene" Bull.Chem.Soc.Jpn.63. 1720-1728 (1990)

[文献書誌] Sachihiko Isoe: "Synthesis of Nepetalactol and Neomatatabiol from (+)ーGenipin"

[文献書誌] Sachihiko Isoe: "Synthesis of (+)ーTecomanin from (+)ーGenipin"

[文献書誌] Eiji Kitamura: "(1R,6R,9S,10S)ー9ーChloroー10ーhydroxyー8ーmethoxycarbonylー4ーmethyleneー2,5ーdioxabicyclo[4.4.0]decー3ーoneー7ーene.A First Chlorineーcontaining Shikimateーrelated metabolite from Fungi" Tetrahedron Lett.31. 4605-4608 (1990)

[文献書誌] Yoshikazu Hiraga: "Facile Synthesis of Regioselective Deuteriated (3R)ー(ー)ー[8,8,8ー^2H_3]Linalool" Chem.Lett.49-52 (1991)

[文献書誌] Shunsuke Izumi: "Synthesis of [10,10,10ー^2H_3]Geranyl Diphosphate" J.Labelled Compd.Radiopharm.印刷中.

[文献書誌] Masamitsu Ochi: "Litophynin D and E,Two New Diterpenoids from a Soft Coral <Litophyton>___ー sp." Chem.Lett.2183-2186 (1990)

[文献書誌] Masamitsu Ochi: "Calicoferols A and B,Two Novel Secosterols Possessing BrineーShrimp Lethality from the Gorgonian <Calicogorgia>___ー sp." Chem.Lett.

[文献書誌] Mitsuaki Kodama: "Convenient Synthesis of Chiral Epoxyisoprenoids by Yeast Reduction" Tetrahedron Lett.31. 4025-4026 (1990)

[文献書誌] 白濱 晴久: "生体機能解明のための化学合成(部分担当)" 化学同人, 253 (1990)

[文献書誌] Daisuke Uemura: "Bioorganic Marine Chemistry,Vol.4" Springer Verlag, 1-30 (1991)

[文献書誌] Minoru Isobe: "Ansamacrolides Recent Progress in the Chemical Synthesis of Antibiotics.Chapter 4,pp103ー134" SpringerーVerlag, 803 (1990)

1990 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)

[文献書誌] Takenori Kusumi: "A Novel Chlorinated Biscembranoid from the Marine Soft Coral <Sarcophyton>_ー <glaucum>_ー" J.Org.Chem.55. 6286-6289 (1990)

[文献書誌] Midori O.Ishitsuka: "Methyl Sarcoate,a Half of the Marine Biscembranoids,from the Soft Coral <Sarcophyton>_ー <glaucum>_ー" Tetrahedron Lett.

[文献書誌] 白濱晴久: "生体機能解明のための化学合成(部分担当)" 化学同人, 253 (1990)