植物ステロール側鎖の生合成機構の精密解析
スポンサーリンク
概要
- 論文の詳細を見る
Campesterol (3) and dihydrobrassicasterol (4), typical C_<28>-sterols in higher plants, are biosynthesized from a steroidal 24-ene precusor (desmosterol 1) via 24-methylenecholesterol (2) and 24-methyldesmosterol (5). A typical plant C_<29>-sterol, sitosterol (6), is produced from 24-methylenecholesterol via isofucosterol (7) and 24-ethyldesmosterol (8). The biosynthetic mechanism, focussing stereochemical features, of these side-chain transformations has been studied in detail by feeding regio- and stereoselectively ^<13>C- or ^2H-labeled steroidal substrates to cell cultures of higher plants such as Oryza sativa, Catharanthus roseus and Morus alba. These studies allowed to correlate the matabolic origin of C-26 and C-27 of the intermediate sterols. It has been established that the 1st methylation leading to 24-methylenecholesterol from desmosterol involves a Re-face hydrogen migration from C-24 to C-25 based on unambiguous assignment of the isopropyl pro-R-Me and pro-S-Me of 24-methylenecholesterol. The 2nd methylation leading to isofucosterol was revealed to proceed in a trans-mechanism in which addition of the methyl group and elimination of the C-28 hydrogen occur on opposite faces of the original Δ^<24(28)> plane. The double bond isomerization from Δ^<24(28)> to Δ^<24(25)> was found to proceed in a syn-S_E2' mechanism with the pro-S-methyl group of isofucosterol becoming the (E)-methyl of 24-ethyldesmosterol. Finally, feeding studies of [E-Me-^<13>C]- and [Z-Me-^<13>C]-24-methyldesmosterols established that an anti-mode of hydrogen addition is operating in the conversion of 24-methyldesmosterol to campesterol and dihydrobrassicasterol. Similar studies established that 24-ethyldesmosterol is converted to sitosterol in an anti-mode of hydrogen addition. In addition, the mechanism of sterol side-chain formation in hairy roots of Ajuga reptans var. atropurpurea is briefly described.
- 2000-10-01
著者
-
池川 信夫
新潟薬科大学
-
森崎 益雄
共立薬大
-
藤本 善徳
東工大院理工
-
藤本 善徳
Department Of Chemistry Tokyo Institute Of Technology
-
藤本 善徳
東京工業大学大学院理工学研究科
-
森崎 益雄
共立薬科大学
関連論文
- 72(P-55) ステロール生合成におけるΔ^オレフィン還元反応の立体化学(ポスター発表の部)
- 32 コール酸生合成におけるステロイド側鎖切断反応(β-酸化)の立体化学(口頭発表の部)
- NON-STEREOSPECIFIC FORMATION OF 3α, 7α, 24-TRIHYDROXY-5β-CHOLESTAN-26-OIC ACID DURING CHENODEOXYCHOLIC ACID BIOSYNTHESIS
- Non-stereoselective Formation of 3α, 7α, 12α, 24-Tetrahydroxy-5β-cholestan-26-oic Acid during Cholic Acid Biosynthesis
- Stereochemistry of Hydrogen Addition to C-25 of Desmosterol by Sterol-Δ^-Reductase of Rat Liver Homogenate
- IDENTIFICATION OF 27-NOR-3α, 7α, 12α-TRIHYDROXYCOPROSTAN-24-ONE APPARENTLY DERIVED FROM 3α, 7α, 12α-TRIHYDROXY-24-OXOCOPROSTANOIC ACID, A POSTULATED INTERMEDIATE OF BILE ACID BIOSYNTHESIS
- Formation of 9,25-Cyclofernane by Reductive Homoallylic Cyclization of Fern-9(11)-en-25-ol Mesylate
- Annonaceous Acetogenins from the Seeds of Annona squamosa.Adjacent Bis-tetrahydrofuranic Acetogenins
- A NOVEL STEROIDAL SAPOGENIN, POGOSTEROL FROM VERNONIA POGOSPERMA
- 功労賞受賞 Masato Tanabe氏の業績
- 植物ステロール側鎖の生合成機構の精密解析
- 津田恭介先生の研究業績
- 津田恭介先生を偲ぶ
- 微量分析30年 : 池川信夫先生にきく
- 薬学会賞受賞 岩崎成夫氏の業績
- 故 岩井一成先生を偲んで
- 大腸がんとビタミンD : 含フッ素1,25-(OH)_2D_3アナログDD-003のin vivo実験
- Fatty Acids and Sterols of the Tunicate, Salpa thompsoni, from the Antarctic Ocean : Chemical Composition and Hemolytic Activity
- Structure of Acrosome Reaction-Inducing Steroidal Saponins from the Egg Jelly of the Starfish, Asterias amurensis(Organic,Chemical)
- Synthesis of 3β, 6α-Dihydroxycholesta-9(11), 17(20), 24-trien-23-one, the Aglycone of Acrosome Reaction-Inducing Steroidal Saponin Co-ARIS II
- 80 昆虫におけるシトステロール側鎖切断反応の中間体フコステロールエポキシドについて
- SYNTHESIS OF β-OXO THIOL ESTERS RELATED TO BILE ACID BIOSYNTHESIS
- Carbon-13 Nuclear Magnetic Resonance of 24-Substituted Steroids
- 54(P1-2) フコステロールエポキシドの酵素的、化学的転位反応のメカニズム(ポスター発表の部)
- Synthesis of Demethylgorgosterol and Its Stereoisomers
- P-1 Acaterinの生合成研究 : Dehydroacaterin reductaseの遺伝子クローニングとその反応機構(ポスター発表の部)
- Identification of 24-Epibrassinolide in Bee Pollen of the Broad Bean, Vicia faba L.
- 活性型ビタミンD (動的天然物化学)
- Angiotensin Converting Enzyme-Inhibitory Triterpenes from Ganoderma lucidim
- Steroidal Inhibitors of Microbial Degradation of Sterol Side Chains
- Stereochemistry in the Hydrogenation of Steroidal(22R)- and (22S)-Δ^-26,22-Lactones
- Pyridine-Induced Deshielding of 4-Methylene Protons for the Determination of C-6 Stereochemistry of Sterols Having a 5α, 6-Diol Moiety. Revision of the C-6 Stereochemistry of Marine Sterol Isolated from a Sponge, Dysidea sp.
- Side Chain Structural Requirement for Utilization of Sterols by the Silkworm for Growth and Development. Non-stereoselective Utilization of the 24-Stereoisomeric Pairs of 24-Alkylsterols
- EFFECTIVE SEPARATION OF STEROL C-24 EPIMERS BY REVERSED-PHASE HIGH PERFORMANCE LIQUID CHROMATOGRAPHY
- 51 Gorgosterolの立体選択的合成
- ステロイド生合成における炭素-炭素結合の切断反応-2-側鎖部における反応について
- ステロイド生合成における炭素-炭素結合の切断反応-1-ステロイドホルモンの生合成について
- Hydrogenolysis of Allylic Alcohols with Mixed Hydride Reagent of Lithium Aluminum Hydride-Titanium Tetrachloride
- OXYGENATED STEROLS AS INHIBITORS OF ENZYMATIC CONVERSION OF DIHYDROLANOSTEROL INTO CHOLESTEROL
- Effects of Cholesterol Analogs on Cholesterol Biosynthesis from Lanosterol
- バンレイシ科植物Annona reticulata種子から得た新規ビステトラヒドロフランアセトゲニンの構造 : 有機化学・天然物化学
- P-61 非直結型ビステトラヒドロフランアセトゲニンの立体化学について(ポスター発表の部)
- Squamosten-A, a Novel Mono-tetrahydrofuranic Acetogenin with a Double Bond in the Hydrocarbon Chain, from Annona squamosa L.
- テトラヒドロフランアセトゲニン類の構造解析--プレカ-サ-イオンスキャン法の適用
- P-35 ゴマノハグサ目植物の腺毛分泌物の化学成分研究(ポスター発表の部)
- 73(P-57) 植物ステロール側鎖生合成機構の解析 : C-28位における反応の立体化学(ポスター発表の部)
- 23 高等植物における24-メチルステロール側鎖の生合成機構の解析(口頭発表の部)
- カイコの休眠卵に見いだされた未同定エクジステロイド, 特に3-エピエクジステロイドの精製と構造解析について
- Annonaceous Acetogenins from the Seeds of Annona squamosa.Non-adjacent Bis-tetrahydrofuranic Acetogenins
- Non-stereoselective Conversion of the Four Diastereoisomers at the C-24 and C-25 Positions of 3α, 7α, 12α, 24-Tetrahydroxy-5β-cholestan-26-oic Acid into Cholic Acid
- Squamocin, a New Cytotoxic Bis-tetrahydrofuran Containing Acetogenin from Annona squamosa
- 23-Hydroxyphysalolactone, a New Withanolide with a 23-Hydroxyl Group from Physalis peruviana (Solanaceae)
- 46 古細菌細胞膜脂質の生合成機構(口頭発表の部)
- Synthesis and Determination of Stereochemistry of Four Diastereoisomers at the C-24 and C-25 Positions of 3α, 7α, 12α, 24-Tetrahydroxy-5β-cholestan-26-oic Acid
- Biological Properties of 20-Isocholesterol
- 活性型ビタミンD
- Preparation of (26-^C)Desmosterol
- テトラヒドロフランアセトゲニン類の構造解析-プレカーサーイオンスキャン法の適用-
- PHOTOCHEMICAL REACTION OF CHOLESTEROL ANALOGS WITH A CARBENE-GENERATING SUBSTITUMENT ON THE SIDE CHAIN
- SYNTHESES OF CHOLESTEROL ANALOGS WITH A CARBENE-GENERATING SUBSTITUENT ON THE SIDE CHAIN
- Free Sterols of the Sea Urchin Echinometra lucunter
- Oxygenated Sterol Derivatives. Their Identification from the Fungus-Infected Silkworm Carcass, Bombyx cum Botryte, and Their Effects on Growth and Sterol Metabolism of the Silkworm, Bombyx mori
- Nutritional Effect of Some Cholestenols and Cholestadienols on the Silkworm Bombyx mori
- High Pressure Liquid Chromatography of Sterol Benzoates