1992 Fiscal Year Annual Research Report

プレニル鎖の鎖延長反応と環化反応における基質一酵素間の精密構造認識と反応機構

Research Project

Project/Area Number	04220228
Research Institution	Hiroshima University
Principal Investigator	菅隆幸広島大学, 理学部, 教授 (00033811)
Co-Investigator(Kenkyū-buntansha)	唐益雄広島大学, 理学部, 助手 (60243549) 平賀良知広島大学, 理学部, 助手 (10238347) 泉俊輔広島大学, 理学部, 助手 (90203116) 太田伸二広島大学, 機器分析センター, 助教授 (60185270)
Keywords	ファルネシルニリン酸合成酵素 / 基質特異性 / アリルニリン酸類 / ホウショウ / (R)-(-)-リナロール生合成 / ハッカ / 酸素官能基導入機構 / (S)-(-)-[9-^3]リモネン
Research Abstract	1.ファルネシルニリン酸(FPP)合成酵素のアリルニリン酸部位に関する基質特異性をゲラニルニリン酸(GPP)のアナログ基質を用いて調べた。一級のcis二重結合をもつネリルニリン酸(NPP)とイソペンテニルニリン酸(IPP)を基質とした場合,trans,cis-FPPが生合成した(収率0.7%)が,その反応性はtrans二重結合をもつGPPの場合(収率83%)に比べて極めて低かった。三級のリナルニリン酸(LPP)とIPPからtrans,trans-FPPが収率4%で生成することが見出されたが,このFPPの生成はLPPの非酵素的異性化によって生成したGPPにIPPが酵素的に縮合したものであることが実証された。すなわち,FPP合成酵素は,SPPとIPPとの反応を触媒しないことが示された。従って,FPP合成酵素のアリルニリン酸部位に関する基質特異性は高いことが明らかとなった。 2.ホウショウにおける(R)-(-)-リナロールの生合成機講をトレーサー実験により解明した。その結果,GPP合成酵素によってIPPとジメチルアリルニリン酸からGPPがまず生合成し,ついで,このGPPが酵素的に加水分解を受ける際に,立体特異的な異性化が同時に生起して(R)-(-)-リナロールを生合成していることがわかった。 3.ハッカの酵素系によるリモネンヘの酸素官能基導入機構を(S)-(-)-[9-^3H]リモネンを用いたトレーサー実験により解明した。その結果,(S)-(-)-リモネンの1位二重結合が立体選択的に酸化されてtrans-リモネン-1,2-ウポキシドが生合成し,ついでこのエポキシドが酵素的に開裂して,(+)-trans-カルベオールを生合成することが実証された。

Research Products
(14 results)

All Other

All Publications (14 results)

[Publications] D.I.Ito: "Facilitation of Diphosphate Group Elimination from Geranyl Diphospghate by Magnesium Ion Chelation in Cyclic Monoterpenoid Biosynthesis" J.Chem.Soc.,Perkin Trans.1,. 1992. 37-39 (1992)
[Publications] Y.Tang: "Biotramsformation of(4R)-(-)-Carvone by the Immobilized Cells of Nicotiana tabacum" J.Sci.Hiroshima Univ.Ser.A. 56. 53-58 (1992)
[Publications] K.Munesada: "Biologically Active Labdane-type Diterpene Glycosides from the Root-stalks of Gleichenia japonica" Phytochemistry. 31. 1533-1536 (1992)
[Publications] T.Endo: "Stereochemistry in the Biosynthesis of Geranyl Diphoshate with Gerany Diphosphate Synthase from Pelargonium roseum" Phytochemistry. 31. 1565-1568 (1992)
[Publications] S.Ohta: "An Efficient Method for Following the Enzymic Reactions Involved in Camphor Biosynthesis in Cinnamomun camphora by Use of GC-MS and Regiospecifically Deuteriated Substrate" J.Labelled Compds.Radiopharm.30. 397-402 (1992)
[Publications] H.L.Siddiqui: "Biologically Active Clerodane-type Diterpene Alcohol and Its Glycosides from the Root-stalks of Ferns" J.Chem.Soc,.Perkin Trans.1. 1992. 781-758 (1992)
[Publications] T.Endo: "Demonstration of Geranyl Diphoshate Synthase in Several Hinger Plants" Phytochemistry. 31. 2273-2275 (1992)
[Publications] Y.-X.Tang: "Characterization of Two Enone Reductases from Nicotiana tabacum Cell Cultures" Phytochemistry. 31. 2599-2603 (1992)
[Publications] T.Suga: "Regioselective Hydrogen Elimination from the 10-Methyl Group of Geranyl Diphosphate in the Biological Formation of the 8(9)-Double Bond of Limonene" J.Chem.Soc.,Chem.Commun.1992. 1556-1558 (1992)
[Publications] T.Suga: "Endogenous Pine-Wood Nematicidal Substances in Pines,Pinus massoniana,P.strobus,and P.palustris" Phytocemistry. 32. (1993)
[Publications] T.Suga: "Selective Hydrogenation of the C-C Double Bond of α,β-Unsaturated Carmonyl Compounds by the Immobilized Cells of Nicotiana tabacum" J.Nat.Prod.56. (1993)
[Publications] Y.Hiraga: "Facile Synthesis of(4S)-(-)-[9- ^3H]Limonene" J.LAbelled Comds.RAdiopharm.31. (1993)
[Publications] Y.Hiraga: "Biosynthetic Generation of Species-specific Cheralty of Limonene by Face-defined Elimination of Diphosphate from Geranyl Diphasphate" J.Chem.Soc.,Chem.Commun.1993. (1993)
[Publications] T.Suga: "Proceedings of the VII Asian Symposium on Medicinal Plants,Spzices,and Other Natural Products" Stereocontrol in the Biosynthesis of Limonene. 129-134 (1992)

1992 Fiscal Year Annual Research Report

プレニル鎖の鎖延長反応と環化反応における基質一酵素間の精密構造認識と反応機構

Principal Investigator

菅 隆幸 広島大学, 理学部, 教授 (00033811)

Research Products

[Publications] D.I.Ito: "Facilitation of Diphosphate Group Elimination from Geranyl Diphospghate by Magnesium Ion Chelation in Cyclic Monoterpenoid Biosynthesis" J.Chem.Soc.,Perkin Trans.1,. 1992. 37-39 (1992)

[Publications] Y.Tang: "Biotramsformation of(4R)-(-)-Carvone by the Immobilized Cells of Nicotiana tabacum" J.Sci.Hiroshima Univ.Ser.A. 56. 53-58 (1992)

[Publications] K.Munesada: "Biologically Active Labdane-type Diterpene Glycosides from the Root-stalks of Gleichenia japonica" Phytochemistry. 31. 1533-1536 (1992)

[Publications] T.Endo: "Stereochemistry in the Biosynthesis of Geranyl Diphoshate with Gerany Diphosphate Synthase from Pelargonium roseum" Phytochemistry. 31. 1565-1568 (1992)

[Publications] S.Ohta: "An Efficient Method for Following the Enzymic Reactions Involved in Camphor Biosynthesis in Cinnamomun camphora by Use of GC-MS and Regiospecifically Deuteriated Substrate" J.Labelled Compds.Radiopharm.30. 397-402 (1992)

[Publications] H.L.Siddiqui: "Biologically Active Clerodane-type Diterpene Alcohol and Its Glycosides from the Root-stalks of Ferns" J.Chem.Soc,.Perkin Trans.1. 1992. 781-758 (1992)

[Publications] T.Endo: "Demonstration of Geranyl Diphoshate Synthase in Several Hinger Plants" Phytochemistry. 31. 2273-2275 (1992)

[Publications] Y.-X.Tang: "Characterization of Two Enone Reductases from Nicotiana tabacum Cell Cultures" Phytochemistry. 31. 2599-2603 (1992)

[Publications] T.Suga: "Regioselective Hydrogen Elimination from the 10-Methyl Group of Geranyl Diphosphate in the Biological Formation of the 8(9)-Double Bond of Limonene" J.Chem.Soc.,Chem.Commun.1992. 1556-1558 (1992)

[Publications] T.Suga: "Endogenous Pine-Wood Nematicidal Substances in Pines,Pinus massoniana,P.strobus,and P.palustris" Phytocemistry. 32. (1993)

[Publications] T.Suga: "Selective Hydrogenation of the C-C Double Bond of α,β-Unsaturated Carmonyl Compounds by the Immobilized Cells of Nicotiana tabacum" J.Nat.Prod.56. (1993)

[Publications] Y.Hiraga: "Facile Synthesis of(4S)-(-)-[9- ^3H]Limonene" J.LAbelled Comds.RAdiopharm.31. (1993)

[Publications] Y.Hiraga: "Biosynthetic Generation of Species-specific Cheralty of Limonene by Face-defined Elimination of Diphosphate from Geranyl Diphasphate" J.Chem.Soc.,Chem.Commun.1993. (1993)

[Publications] T.Suga: "Proceedings of the VII Asian Symposium on Medicinal Plants,Spzices,and Other Natural Products" Stereocontrol in the Biosynthesis of Limonene. 129-134 (1992)

菅隆幸広島大学, 理学部, 教授 (00033811)