7 インドール誘導体の合成研究 : dl-Aspidospermine合成中間体の立体構造並びにAspidospermine立体異性体(dl-)の合成

スポンサーリンク

概要

• 論文の詳細を見る

• The total syntheses of dl-aspidospermine (Ia) were reported by Stork et al. in 1963 and by Ban et al. in 1964. The key intermediates of the same plane formulas(II and III) in both syntheses were prepared in independent ways, whose physico-chemical properties were quite different. At first, IIa and IIIa were given by Stork to his compounds, and accordingly IIb and IIIb corresponding to the conformation of IIb were preferred by us to our compounds on taking the above assignment into consideration, although the possibility of IIa to our compound was alternatively deduced based on n.m.r. spectral data. For clarification of this point, trans-decahydroquinolone(VI) was synthesized by the method of Grob and derived to VII, whose n.m.r. spectra were compared with the corresponding compounds including II, XI-A and XI-B. In addition, the fact that the intramolecular hydrogen bonding was observed with XIII-B and not with XIII-A, concludes that our intermediates(II and XI-A) are of A/B trans and the Stork's compound(II) and XI-B are of A/B cis. Subsequently, the fused form of C-ring to A- and B- rings in II and III was carefully investigated, and in conclusion IIc and IIIa were given to our intermediates. From IIIa, there were synthesized dl-aspidospermide and the other diastereoisomer of the natural alkaloid, the structure, of the latter was elucidated by X-ray crystallography to be XXVIII, which is compatible with the above assignment to our intermediates.

• 天然有機化合物討論会の論文
• 1967-09-25

著者

• 大石 武

  北大・薬:(現)理化学研究所

• 坂部 知平

  名大理学部

• 仙藤 宥二

  塩野義研

• 伴 義雄

  北大薬学部

• 大石 武

  北大薬学部

• 赤木 昌夫

  北大薬学部

• 飯島 郁夫

  北大薬学部

• 飯島 郁夫

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 仙藤 宥二

  北大薬学部

関連論文

• The Synthesis of 3-Spirooxindole Derivatives. IX. The Reactions of 2-Hydroxytryptamine with Hemiacetals
• 72 光フリース転位反応を利用したインドールアルカロイドの合成研究
• 63 分子内閉環による7α-メトキシ-1-オキサセフェム骨格の新しい立体制御的合成
• 13 IBOGA ALKALOIDSの合成研究 : dl-Ibogamine,dl-Epiibogamine dl-Ibogaine,dl-Epiibogaine,dl-Tabernanthine,dl-Epitabernanthineの全合成
• 34 dl-Epiibogamineの全合成
• 7 Aspidosperma及びIboga alkaloidsの合成研究
• 20.Aspidosperma及びIboga alkaloidsの合成研究
• A Synthesis of (±)-Dihydrodeoxyepiallocernuine by Application of a Facile Hofmann-Loeffler Type of Photocyclization
• Infrared Spectra of Some Indole and Pyrrole Compounds
• Reaction of 1-Phenethyl-2 (1H)-pyridones with Phosphoryl Chloride. Formation of 1-Phenethyl-2-chloropyridinium Salts.
• The Reactions of Activated Amides. I. The Reactions of Iminoethers derived from the Secondary Amides with the Nucleophiles
• 21 オキシインドール誘導体よりアスピドスペルマおよびイボガアルカロイドの合成に関する研究
• The Fischer Indole Synthesis with Formic Acid.I.A Convenient Synthesis of 4a-Ethyl-9-formyl-1,2,3,4,4a, 9a-hexahydro-9H-carbazole
• Activation of Weak Organic Bases. VI. The Alkylation of Thiol Esters by Triethyloxonium Salt and Diethoxycarbonium Salt (HC^^+(OC_2H_5)_2,S^^-bCl_6)
• 1.ヨヒンビンの絶対配置とオキシインドール系アルカロイドとの関係
• 21 多環系インドールアルカロイドの合成研究 : (±)-Deoxyaspidodispermineおよび(±)-1-Acetylaspidoalbidineの全合成
• 7 インドール誘導体の合成研究 : dl-Aspidospermine合成中間体の立体構造並びにAspidospermine立体異性体(dl-)の合成
• The Reactions of Activated Amides. VI. The Reactions of 1-Methyl-2-pyrrolidone Dimethylacetal and 2-Methylmercapto-1-methyl-2-pyrroline with Dimethyl Acetylenedicarboxylate
• The Fischer Indole Synthesis with Formic Acid. II. The Synthesis of Hexahydrocyclopent (b) indoles
• The Synthesis of 3-Spirooxindole Derivatives. VIII. Total Syntheses of (±)-Formosanine, (±)-Isoformosanine, (±)-Mitraphylline and (±)-Isomitraphylline
• The Synthesis of 3-Spirooxindole Derivatives. VII. Total Synthesis of Alkaloids (±)-Rhynchophylline and (±)-Isorhynchophylline
• 41 3-Spirooxindoleの誘導体の合成研究 : dl-Formosanine,dl-Isoformosanine,dl-Mitraphylline,dl-Isomitraphyllineの全合成
• 36 3-Spirooxindole誘導体の合成研究 : (±)Rhynchophyllineおよび(±)Isorhynchophyllineの立体選択的合成
• The Reactions of Activated Amides. V. The Reactions of Cyclic Amide Acetals with Electrophiles
• Activation of Weak Organic Bases. V. The Alkylation of Thiono Esters by Diethoxycarbonium Hexachloroantimonate [chemical formula], S^^-bCl_6
• Activation of Weak Organic Bases. III. The Reactions of Divalent Sulfides with Acid Chlorides in the Presence of Friedel-Crafts Catalysts
• The Reactions of Activated Amides. IV. The Reactions of Amide Acetals with Esters
• The Synthesis of 3-Spirooxindole Derivatives. IV. The Conversion of 3-Spirooxindole to Indole Derivative.
• The Synthesis of 3-Spirooxindole Derivatives. III. Stereospecific Syntheses of rac-N-Methylrhynchophyllane for Stereochemistry of Rhynchophylline and Isorhynchophylline.
• The Synthesis of 3-Spirooxindole Derivatives. II. Syntheses of 1-Methylspiro-[indoline-3,1'-pyrrolizidine and Indolizidine]-2-one.
• The Synthesis of 3-Spirooxindole Derivatives. I. Syntheses of 1-Methyl-2', 3', 10', 10'a-tetrahydrospiro [indoline-3,1' (5'H)-pyrrolo [1,2-b]-isoquinoline]-2-one and its Homologs.
• The Preparation of 2-(Substituted phenyl) ethanols.

もっと見る 閉じる

スポンサーリンク