2 Trichothecene型sesquiterpene類の全合成

スポンサーリンク

概要

• 論文の詳細を見る

• Total synthesis of (±)-12,13-epoxytrichothec-9-ene (V), isolated from the metabolite of Trichothecium roseum by Nozoe et al, was accomplished.The keto-ester (VI) was reacted with crotonaldehyde to give a keto-aldehyde which was converted into the acetal (VII). The Meerwein-Ponndorf reduction of VII gave the cis-fused pyrane derivative (VIII). Reduction of VIII with LiAlH_4 afforded an alcohol (IX) which without purification was submitted to the next reaction because the alcohol (IX) was easily transformed to the compound (X) by silica gel chromatography. Tosylation of IX with p-TsCl-pyridine, followed by treatment of the resulting tosylate with LiAlH_4 gave the methyl derivative (XII). Selective attack of XII by m-chloroperbenzoic acid produced a diastereomeric mixture of the hydroxy ester (XIII) which was pyrolysed to the ketone (XIV). Allylation of XIV with allyl bromide did not give the C-alkylated product, but gave an unexpected O-alkylated compound (XVI). Rearrangement of XVI was accomplished by heating to give a mixture of XVII and XVIII in a 1:2 ratio. Treatment of XVIII with OsO_4-KClO_3 afforded the diol(XIX) which was cleaved by NaIO_4 to yield the keto-aldehyde monohydrate (XX). XX was cyclized with NaOMe to give a diastereomeric mixture of the tricyclic ketol (XXI) which was converted into the keto-iodide(XXV) by the action of (PhO)_3PMeI. Reduction of XXV with Raney-Ni gave the ketone (XXVII), while treatment of XXV with Zn-EtOH gave an undesired ketol (XXVI). Reaction of XXVII with dimethyloxosulfonium methylide produced an epimer (XXVIII) of 12,13-epoxytrichothec-9-ene. The Wittig reaction of XXVII with methylene triphenylphosphorane gave the corresponding methylene compound (XXIII) which was treated with m-chloroperbenzoic acid to afford (±)-12,13-epoxytrichothec-9-ene(V) after purification by preparative thin layer chromatography. The IR and NMR spectra of the final product was superimposable on that of the authentic sample kindly provided by Dr. S. Nozoe.

• 天然有機化合物討論会の論文
• 1974-10-01

著者

• 辰野 高司

  理化学研究所

• 藤本 康雄

  The Institute Of Physical And Chemical Research

• 辰野 高司

  Institute of Physical and Chemical Research

• 藤本 康雄

  理研

• 辰野 高司

  理研

• 与倉 進

  理研

• 中村 忠治

  理研

• 森川 民雄

  理研

• 森川 民雄

  理研:(現)田辺製薬東京研究所

• 中村 忠治

  理研:(現)日本ケミファー(株)

• 与倉 進

  理研:(現)東京理科大学薬学部

関連論文

• Studies on the Racemization of Amino Acids and Their Derivatives. III. The Effect of Alkyl-, Aralkyl- and Aryl-Side Chain at α-Position of Amino Acids on Their Base-Catalyzed Racemization
• Studies on the Racemization of Amino Acids and Their Derivatives. II. On the Deuterium-Hydrogen Exchange Reaction of Amino Acid Derivatives in a Medium of Deuterated Acetic Acid
• Simultaneous Determination of N- and C-Terminal Amino Acids in Polypeptides : Selective Tritiation of DNP-Peptides
• アミノ酸誘導体のラセミ化に関する研究(第4報) : 酢酸中におけるアミノ酸のラセミ化速度と構造の関連について
• Synthesis of D-Alanine under the Asymmetric Induction due to Molecular Asymmetry
• The C-Terminal Determination of Polypeptide by the Selective Tritium-labeling. V. C-Terminal Cleavage of Peptide by the Action of Acetic Anhydride
• Studies on the Metabolites of Penicillium diversum var. aureum. I
• Studies on the Biological Activities of Islandic Acid and Related Compounds
• Studies on the Constituents of Artemisia argyi LEVL et VANT
• 22 Penicillium diversum var aureumの生産する抗腫瘍性代謝産物について
• 紅足蒿(Artemisia rubripes NAKAI)の成分研究
• LEAD (IV) ACETATE-METAL HALIDE REAGENTS II. A NEW METHOD FOR THE SYNTHESIS OF β-HALO CARBOXYLATES AND β-IODO ETHERS
• 83 Penicillium islandicum Soppの生産するDNA合成阻害物質の構造
• Recherche Toxicologique des Substances Metaboliques de Penicillium carneo-lutescens
• Modification of α-Santonin. IV. Epoxidation of Germacranolide-type Sesquiterpenes
• Modification of α-Santonin. III. Synthesis of Dihydrocostunolide
• 微生物によるSantonin誘導体の構造変換
• 23 α-SantoninからGermacrane型化合物への変換 : Dihidrocostunolideの合成
• 2 Trichothecene型sesquiterpene類の全合成
• Recherches Toxicologiques sur les Substances Toxiques de Fusarium nivale : Etude Chimique des Toxins Principales, Nivalenol, Fusarenon-X et Nivalenol-4,15-di-O-acetate
• 31 麦赤カビ病菌Fusarium nivale代謝有毒成分の中毒学的検討(第6報) : Nivalenol及びその関連化合物の化学構造に関する研究
• Recherches Toxicologiques des Substances Metaboliques du Fusarium nivale. II. Effet Antileucemique du Nivalenol et du Dihydronivalenol
• 4. Thiadiazol urea誘導体の合成とその殺草活性について
• Studies on Aminobutenolide Compounds. I. The Reaction of o-Phthalaldehydic Acid with Amino Compounds
• 日本のマイコトキシン研究を回顧し,伝えたいこと
• 教育賞受賞 山川浩司氏の業績
• フランスの医薬分業の現状と歴史(諸外国の医薬分業の現状)
• 諸外国における薬剤師試験制度
• 「薬学教育問題について」
• 薬の歴史 : 薬学の成立とその発展(医薬品を考える)
• "個人の衛生環境によって変動する薬物活性"の問題を誰が扱うのか(衛生薬学領域における教育はいかにあるべきか)
• 慶松勝左衛門
• 共通の概念規定のもとに全薬学人が議論する習慣をもとう
• Chemical Studies on Chlorine-containing Peptide-One of the Toxic Metabolites of P. islandicum Sopp. I. Structure and Synthesis of Dehydrochlorinated-Peptide Amide
• STRUCTURES OF SECOJESACONITINE AND SUBDESCULINE, TWO NEW DITERPENOID ALKALOIDS FROM ___- ___- THUNB.
• 66(PA2-6) 高度に酸化されたα-ピロン誘導体の合成と抗腫瘍活性 : Islandic Acid I Methyl Ester,RosellisinおよびRosellisin Aldehydeの全合成(ポスター発表の部)
• フザリウム産出毒素のカブレ
• 5-Lipoxygenase Inhibitors Isolated from Gardeniae Fructus
• STRUCTURE-ACTIVITY CONSIDERATION OF NOVEL ANTICANCER PLATINUM PYRIMIDINE "GREENS"(Communications to the Editor)
• 3-CAFFEOYL-4-SINAPOYLQUINIC ACID, A NOVEL LIPOXYGENASE INHIBITOR FROM GARDENIAE FRUCTUS(Communication to the Editor)
• ISOLATION AND STRUCTURAL ELUCIDATION OF A NEW LIPOXYGENASE INHIBITOR FROM GARDENIAE FRUCTUS
• AN EFFICIENT AND STEREOCONTROLLED SYNTHESIS OF A CIS-AND TRANS-FUSED BICYCLO [5.4.0] UNDECANE RING SYSTEM VIA INTRAMOLECULAR [2+2] PHOTOCYCLOADDITION
• 95(PB3-6) インドネシア産植物Artocarpus communis中のリポキシゲナーゼ活性阻害物質について(ポスター発表の部)
• A new Cytotoxic Chlorine-Containing Polyacetylene from the Callus of Panax ginseng
• Studies on the Metabolites of Penicillium diversum var. aureum. II. : Synthesis and Cytotoxic Activity of Trihydroxytetralones
• (96) カンキツ黒点病ならびに軸腐病の発病機構に関する研究(30) : カンキツ果皮から単離された抗菌性物質について (昭和62年度日本植物病理学会大会講演要旨)

もっと見る 閉じる

スポンサーリンク