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

スポンサーリンク

概要

• 論文の詳細を見る

• The total synthesis of the entitled poly-cyclic indole alkaloids has been achieved from a common intermediate. (1) Total synthesis of (±)-deoxyaspidodispermine(1) Compound(6) was prepared from 2-hdyroxytryptamine and its stereochemistry fully elucidated. It was treated with oxygen at -78°for 2 hr in a solution of NaH in Bu^tOH and dimethylformamide containing triethyl phosphite to give the hydroxy-derivatives [7a(51%) and 7b(5%)]. The ketol(7a) was reduced with LiAlH_4 in DME by refluxing for 1 hr to furnish 8 (31%) with 9a and 9b. The compound(8) was acetylated and hydrogenated with Adams' catalyst to give (±)-deoxyaspidodispermine(1), which was identified with the authentic sample of the natural alkaloid. (2) Total synthesis of (+)-1-acetylaspidoalbidine(10) Compound(6) was submitted to the Michael condensation with ketene thioacetal monoxide in DME containing lithium diisopropylamide at room temperature for 2 hr to afford 15a (38%) and 15b (37%), a mixture of which was hydrolyzed by refluxing for 0.5-1.5 hr in aqueous acetonitrile containing perchloric acid to give the corresponding aldehyde(17) in a quantitative yield. The aldehyde (17) was reduced with LiAlH_4 to give the alcohol (18), which was acetylated and hydrogenated with Adams' catalyst, affording 21 as an amorphous solid. On oxidation with mercuric acetate, 21 gave (±)-1-acetylaspidoalbidine(10), which was identical with the authentic specimen of the natural alkaloid.

• 天然有機化合物討論会の論文
• 1974-10-01

著者

• 大沼 毅

  北大・薬:(現)ブリストル・マイヤーズ研究所(株)

• 伴 義雄

  東邦大・薬

• 伴 義雄

  北大薬

• 伴 義雄

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 大石 武

  北大・薬:(現)理化学研究所

• 大石 武

  北大薬学部

• 大沼 毅

  北大薬学部

• 関 興一

  北大薬

関連論文

• 61 十字交差環化反応を用いるアルカロイド類の合成
• The Synthesis of β-Carboline Derivatives. VII. The Isolation of the Possible Intermediate in the Condensation of 3-(2-Bromoethyl) indole and 2-Halogenopyridine.
• The Synthesis of 3-Spirooxindole Derivatives. IX. The Reactions of 2-Hydroxytryptamine with Hemiacetals
• 63 Pyrrolo-1,4-benzodiazepine系抗生物質の合成
• 63 Pd触媒による一酸化炭素挿入反応を利用した1,4-Benzodiazepine骨格の合成並びにその天然物合成への応用
• 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
• Alkylated Levoglucosan in Organic Synthesis. : A Formal Total Synthesis of Elaiophylin
• Studies on the Bischler-Napieralski Reaction with Unsaturated Lactams. Syntheses of 5,6,9,10,11,12-Hexahydro-2,3-dimethoxybenzo [4,5-a]-benzo [f] quinolizinium and Dihydrosempervirine Salts
• 64(PA2-4) 抗腫瘍活性物質エリオラニンの合成研究(ポスター発表の部)
• 44 二量体マクロリドの合成研究
• 環拡大によるラクトン環の形成とジプロジアリドおよびホラカンソリドの合成 (中・大環状天然物合成の新展開) -- (ラクトンおよびラクタムの形成反応とマクロリドおよびその関連化合物の合成)
• アシロイン縮合反応を用いた天然物の合成 (天然物化学1980B)
• 41 ステロイド水酸化阻害物質,diplodialides及び関連化合物の合成
• 生合成類似の有機合成反応--主としてインド-ルアルカロイドについて (酵素類似機能をもつ有機反応-2-)
• 59 1,2-Enediolateの反応を利用した天然物の合成研究
• 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
• Studies on the Structures of Some Cholestanoindoles
• The Absolute Configuration of Sarkomycin.
• Quinolizidines. VII. Structure of O-Methylpsychotrine : The Endocyclic versus the Exocyclic Double Bond Structure in the Dihydroisoquinoline Moiety
• New Synthesis of Pyrrolo-1,4-benzodiazepines by Utilizing Palladium-Catalyzed Carbonylation
• 36 Pd触媒による一酸化炭素挿入反応を用いた天然物の合成
• 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.
• 18 マイトマイシン類の合成研究 : デカルバモイルオキシマイトマイシン誘導体の合成(口頭発表の部)
• 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
• インド-ルアルカロイドの合成研究(学術研究の動向)
• 窒素を含む天然物の有効利用 (ナイトロジェン・ファインケミカルズの新局面)
• 窒素有機資源の開発と有効利用に関する化学的研究(学術研究の動向)
• ナイトロジェン・ファインケミカルズの一断面 (ナイトロジェン・ファインケミカルズ--窒素有機資源の開発と有効利用)
• Fluorescence and Structure of Proteins as measured by Incorporation of Fluorophore. II. Synthesis of Maleimide Derivatives as Fluorescence-Labeled Protein-Sulfhydryl Reagents.
• Polyphosphate Esters as a Synthetic Agent. III. Amide and Peptide Syntheses
• Studies on Protein-Sulfhydryl Reagents. I. Synthesis of Benzimidazole Derivatives of Maleimide ; Fluorescent Labeling of Maleimide.
• 新しい間接的電解還元法によるアレンスルホニル基の除去--1-ベンツアゾシノン類の合成とその立体配座異性体について (電気エネルギ-を利用する有機合成特集号)
• マイトマイシン関連物質の合成 (「医薬品開発をめぐる生理活性物質の合成」特集号)
• 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 Synthesis of β-Carboline Derivatives. VI. A Synthesis of 3-Ethyl-10-methoxy-12H-indolo [2,3-a] quinolizinium Salt (10-Methoxy-flavopereirine)
• 59 多環系インドールアルカロイドの合成研究 : 2,3のaspidosperma系アルカロイドの全合成並びに二量体型アルカロイド合成の試み
• 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.
• Polyphosphate Ester as a Synthetic Agent. VII. The Beckmann Rearrangement and Formation of Amidines with PPE
• Polyphosphate Ester as a Synthetic Agent. IV. A Novel Preparation of Aryl Esters
• Polyphosphate Ester as a Synthetic Agent. V. The Fischer Indole Synthesis with Polyphosphate Ester
• 新しい間接的電解還元法によるアレンスルホニル基の除去 : 1-ベンツアゾシノン類の合成とその立体配座異性体について
• マイトマイシン関連物質の合成
• 有機金属錯体を用いるヘテロ環の合成 (ヘテロ環の化学)
• PdII-PPh3を用いるCO挿入反応
• The Reactions and Syntheses with Organometallic Compounds. II. The Deallylation Reaction with Pd^ and a New Synthesis of Primary Amines
• The Synthesis of β-Carboline Derivatives. IX. Syntheses of 2-(1-Hydroxymethyl-propyl)-1,2,3,4,6,7-hexahydro-12H, 12bH-indolo [2,3-α]-quinolizine (10-Desoxy-18,19-dihydro-15-epi-hunterburnine)
• The Synthesis of β-Carboline Derivatives. VIII. Syntheses of Bisnorflavocarpine and Its Relatives
• A Synthesis of Dibenzo (a, h) quinolizidine System by way of Immonium Salt Intermediate
• Polyphosphate Ester as a Synthetic Agent. VI. The Bischler-Napieralski Reaction of Tryptamine and Tryptophan Derivatives by Means of Polyphosphate Ester
• Studies on the Structure of (+)-Rubremetinium Cation. A New Synthesis of C-Bisnor-rubremetinium Cation and its Model Compound
• Polyphosphate Esters as Synthetic Reagent. I. Synthesis of 2-Substituted Benzimidazoles
• The Synthesis of β-Carboline Derivatives. V. A Synthesis of 1-Methyl-1,2,3,4,7,8-hexahydro-13H-benz [g] indolo [2,3-a] quinolizinium Salts.
• The Synthesis of β-Carboline Derivatives. IV. Total Synthesis of Alstoniline
• The Synthesis of β-Carboline Derivatives. III. A Synthesis of 10-Methoxy-6,7-dihydro-12H-indolo [2,3-a] quinolizinium Salts.
• 天然物の全合成 : アルカロイドからテルペンまで
• 電極反応を利用した複素環の合成 : 位置ならびに立体選択的合成への道
• 日本薬学会へのメッセージ

もっと見る 閉じる

スポンサーリンク