57 1,6-ジヒドロ-3(2H)-ピリジノンを合成素子とするアルカロイド合成 : (±)-Ibogamine,(±)-Epiibogamine,及び(±)-Tecomanineの全合成

スポンサーリンク

概要

• 論文の詳細を見る

• As parts of the continuous studies on various alkaloids syntheses using a common synthon, ethyl 1,6-dihydro-3(2H)-pyridinone-1-carboxylate (1), we have achieved total synthesis of (±)-ibogamine (6), (±)-epiibogamine (7), and (±)-tecomanine (9) as follows. 1. Total Synthesis of 6 and 7 The alcohol (11) which had been obtained from 1 was transformed to the benzyl urethane (12). Hydrolysis of 12 followed by condensation with the ylid of triethyl phosphonoacetate yielded 14, which was oxidized to the keto ester (10). The base-catalyzed intra-molecular Michael addition of 10 gave 18a and 18b. The isomer (18a) was also obtained as the main product in the following sequence: 21→22→23→18a,b. Both the isomers were converted to the pentacyclic intermediates (32a,b) by several steps. An efficient one-step synthesis of (±)-ibogamine (6) and (±)-epiibogamine (7) from 32a and 32b, respectively, was able to be accomplished with a lithium aluminum hydride-aluminum chloride. 2. Total Synthesis of 9 Reaction of 1 with MeMgI gave 34 with a small amount of 33. Treatment of the former with ethyl propenyl ether in the presence of Hg(OAc)_2 at 200°afforded the aldehyde (52), which was derived to the diketone (58a,b) by the several steps via 56a,b. A careful treatment of 58a,b with K_2CO_3 in ethanol at 45-50°gave the desired product (60) as a sole isomer in 87-88% yield. Reduction of 60 with LiAlH_4 and subsequent oxidation with PCC gave (±)-tecomanine (9). Thus, the first and stereoselective total synthesis of 9 has been achieved.

• 天然有機化合物討論会の論文
• 1981-09-10

著者

• 今西 武

  Faculty Of Pharmaceutical Sciences Osaka University

• 八木 典幸

  Faculty Of Pharmaceutical Sciences Kanazawa University

• 花岡 美代次

  金沢大薬

• 新 広昭

  Faculty of Pharmaceutical Sciences, Kanazawa University

• 新 広昭

  Faculty Of Pharmaceutical Sciences Kanazawa University

• 今西 武

  金沢大薬

• 八木 典幸

  金沢大薬

• 新 広昭

  金沢大薬

関連論文

• Synthetic Studies on Aphidicolane and Stemodane Diterpenes. IV.A Stereoselective Formal Total Synthesis of (±)-Aphidicolin
• Synthetic Studies on Aphidicolane and Stemodane Diterpenes. III.An Alternative Stereoselective Access to Aphidicolane-Type B/C/D-Ring System
• 61 アフィディコラン型およびステモダン型ジテルペンの合成研究(ポスター発表の部)
• Synthesis and Evaluation of Novel Thiazolidine Derivatives as Thromboxane A_2 Receptor Antagonists
• Synthetic Studies on Aphidicolane and Stemodane Diterpenes. II. Neighboring Hydroxyl Group Participation in Stereoselective Syntheses of Tricyclo[6.3.1.0^]dodecanes Corresponding to the B/C/D-Ring Systems
• Synthetic Studies on Spiroketal Natural Products. V. Total Synthesis of (+)-Talaromycin A and (-)-talaromycin B
• Synthetic Studies on Spiroketal Natural Products. IV.A Stereoselective Synthesis of (3S, 5S, 6R, 9R, R_S)-3-Benzyloxymethyl-9-hydroxymethyl-5-(p-tolyl)sulfinyl-1,7-dioxaspiro[5.5]undecane, a Key Intermediate for Talaromycins
• Synthetic Studies on Spiroketal Natural Products. II. An Enantioselective Synthesis of (R)- and (S)-1,7-Dioxaspiro[5.5]undecane
• Synthetic Studies on Spiroketal Natural Products. I. : A Stereoselective Synthesis of (2R^*, 5R^*)- and (2R^*, 5S^*)-2-Methyl-1,6-dioxaspiro[4.5]decane
• Synthetic Study on Gymnomitrol. II. A Synthesis of (±)-Isogymnomitrol
• Synthetic Study on Gymnomitrol and Related Compounds. I.Preparation and Cyclopropane Ring Opening of 1,2,6-Trimethyltetracyclo[5.3.1.0^.0]undecan-9-one
• 7,7-Dimethyltricyclo[3.3.0.0^]octan-3-ones as Synthetic Intermediates. VI. An Improved Formal Synthesis of (±)-Descarboxyquadrone via Highly Regioselective Cyclopropane Ring Opening of Tricyclo[3.3.0.0^]octan-3-one
• 100(P24) 抗腫瘍性スチリルラクトン化合物の高立体選択的合成(ポスター発表の部)
• 1,6-Dihydro-3 (2H)-pyridinones. II. Synthesis of 2-Azabicyclo [2. 2. 2] octanes by the Reaction of N-Substituted 1,6-Dihydro-3 (2H)-pyridinones with 1,3-Dicarbonyl Compounds
• 1,6-Dihydro-3 (2H)-pyridinones. I. Facile Synthesis of N-Substituted 1,6-Dihydro-3 (2H)-pyridinones
• 2-Oxo-1,2,3-oxathiazolidines. Its Application to Separation of Diastereoisomers of β-Amino-alcohols, 6-(4-Methoxy-2-piperidyl)-1,4-dioxaspiro [4,5] decan-6-ol and 2-Hydroxy-2-(2-piperidyl) cyclohexanone
• Synthetic Studies on Securitinine and Related Compounds. II. A Synthesis of 10a-Episecuritinine
• Synthetic Studies on Securitinine and Related Compounds. I. Stereochemistries of the Catalytic Hydrogenation Products of 6-(4-Methoxy-2-pyridyl)-1,4-dioxaspiro [4,5] decan-6-ol
• Transformation of (±)-Ophiocarpine and (±)-13-Epiophiocarpine to (±)-α- and (±)-β-Hydrastine with Complete Retention of Configuration
• Platelet Anti-aggregant Activity of 2,2-Dimethylthiazolidine Hydrochloride and 2-(4-Hydroxy-3-methoxyphenyl)thiazolidine
• Octahydro-7 (1H)-quinolones. VII. A Stereoselective Synthesis of cis, trans-Decahydro-3H, 8H-benzo [i, j] quinolizine-3,8-dione
• 10 リコポジウムアルカロイドの合成研究 : (±)-Anhydrolycodoline及び(±)-Lycopodineの全合成
• A FORMAL TOTAL SYNTHESIS OF (±)-QUADRONE
• Nucleotide Sequences of Membrane-Bound Hydrogenase Gene in Alcaligenes hydrogenophilus
• 54 8,14-Cycloberbineを経由するProtoberberineアルカロイドからSpirobenzylisoquinoline及びBenzindenoazepineアルカロイドの合成
• Synthetic Studies on Spirovetivane Phytoalexins. III. : A Total Synthesis of (±)-Lubiminol
• Synthetic Studies on Spirovetivane Phytoalexins. II. : Stereoselective Synthesis of (2RS, 5RS, 6SR, 8RS, 10SR)-6-Hydroxymethyl-8-methoxymethoxy-10-methyl-2-pivaloyloxyspiro[4.5]decane
• Asymmetric Cyclopropanation by Reaction of a γ-Chloromethylated Chiral Vinylic Sulfoxide with Allylmagnesium Bromide
• Synthetic Studies on Spirovetivane Phytoalexins. V. : A Stereoselective Total Synthesis of (±)-Oxylubimin
• Synthetic Studies on Spirovetivane Phytoalexins. IV. : A Stereoselective Synthesis of (±)-3-Hydroxysolavetivone
• 7,7-Dimethyltricyclo[3.3.0.0^]octan-r-ones as Synthetic Intermediates. V. : An Improved Synthesis of (±)-Pentalenene
• 7,7-Dimethyltricyclo[3.3.0.0^]octan-3-ones as Synthetic Intermediates. IV. : A Further Examination of Cyclopropane Ring Opening in the Tricyclo[3.3.0.0^]octan-3-one System
• Synthetic Studies on Spiroketal Natural Producys. III. : Enantioselective Synthesis of 1,6-Dioxaspiro[4.5]decane Compounds
• 1,6-Dihydro-3 (2H)-pyridinones. V. Total Synthesis of (±)-Eburnamonine
• 1,6-Dihydro-3 (2H)-pyridinones. IV. Synthesis of (±)-Tabersonine and (±)-Cleavamine via a Common Intermediate, Ethyl 3-Ethyl-3-hydroxy-1,2,3,6-tetrahydropyridine-1-carboxylate
• 1,6-DIHYDRO-3 (2H)-PYRIDINONES AS SYNTHETIC INTERMEDIATES. TOTAL SYNTHESIS OF (±)-EBURNAMONINE
• 1,6-Dihydro-3 (2H)-pyridinones as Synthetic Intermediates. A Convenient Total Synthesis of (±)-Cleavamine
• 7,7-Dimethyltricyclo[3.3.0.0.^]octan-3-ones as Synthetic Intermediates. I. : Preparation and Cyclopropane Ring Opening of 7,7-Dimethyl-5-(2-propenyl)tricyclo[3.3.0.0^]octan-3-one
• 1,6-Dihydro-3 (2H)-pyridinones. VIII. Total Synthesis of (±)-Corynantheidol and Formal Synthesis of (±)-Quinine
• 1,6-Dihydro-3 (2H)-pyridinones. VI. Introduction of an Amidocarbonylmethyl Chain at C-4 of the 1,6-Dihydro-3 (2H)-pyridinone Nucleus via Photochemical [2+2] Cycloaddition Reaction
• 1,6-DIHYDRO-3 (2H)-PYRIDINONES AS SYNTHETIC INTERMEDIATES. STEREOSELECTIVE SYNTHESIS OF (±)-CORYNANTHEIDOL AND (±)-QUININE
• Octahydro-7 (1H)-quinolones. IV. Construction of Decahydro-3H, 10H-benzo [i, j] quinolizine-3,10-dione Systems from cis-and trans-Octahydro-7 (1H)-quinolone
• Octahydro-7 (1H)-quinolones. III. cis-trans Isomerization of Octahydro-7 (1H)-quinolone Analogues
• Octahydro-7 (1H)-quinolones. II. A Stereoselective Synthesis of cis-Octahydro-7 (1H)-quinolone
• Octahydro-7 (1H)-quinolones. I. Stereochemistries of Catalytic Hydrogenation of 7-Hydroxyquinoline
• NOVEL AND CHIRAL HANTZSCH-TYPE 1,4-DIHYDROPYRIDINES HAVING A p-TOLYLSULFINYL GROUP. SYNTHESIS AND BIOLOGICAL ACTIVITIES AS CALCIUM CHANNEL ANTAGONISTS
• 1,6-Dihydro-3 (2H)-pyridinones. X. 2-Azabicyclo [2.2.2] octane Ring Formation via Intramolecular Michael Reaction : Total Synthesis of (±)-Ibogamine and (±)-Epiibogamine
• 1,6-Dihydro-3 (2H)-pyridinones. VII. Stereoselective Total Synthesis of a Monoterpene Alkaloid, (±)-Tecomanine
• 1,6-Dihydro-3 (2H)-pyridinones. III. A Formal Synthesis of (±)-Catharanthine
• 57 1,6-ジヒドロ-3(2H)-ピリジノンを合成素子とするアルカロイド合成 : (±)-Ibogamine,(±)-Epiibogamine,及び(±)-Tecomanineの全合成
• 44 1,6-ジヒドロ-3(2H)-ピリジノンを合成素子とするインドールアルカロイド類の合成研究
• 1,6-Dihydro-3 (2H)-pyridinones. IX. A Regioselective Synthesis of Ethyl 3-Methoxycarbonylmethyl-4-oxopiperidine-1-carboxylate from Ethyl 3-Hydroxy-1,2,3,6-tetrahydropyridine-1-carboxylate
• 7,7-Dimethyltricyclo[3.3.0.0^]octan-3-ones as Synthetic Intermediates. III. : Total Synthesis of (±)-Descarboxyquadrone
• 7,7-Dimethyltricyclo[3.3.0.0^]octan-3-ones as Synthetic Intermediates. II. : A Total Synthesis of (±)-Pentalenene, an Angular Triquinane Sesquiterpene
• Synthetic Studies on the Lycopodium Alkaloids. III. Synthesis of a Key Intermediate, Ethyl Octahydro-4aβ-hydroxy-7β-methyl-10-oxo-1H-5,8α-propanoquinoline-1-carbamate, for the Lycopodium Alkaloids
• Synthetic Studies on the Lycopodium Alkaloids. II. A Synthesis of a Key Intermediate, 2,3,5,6,7,8-Hexahydro-7β-methyl-3-oxo-1H-5,8a-propenoquinoline, for the Lycopodium Alkaloids
• Preparations and Stereochemistries of Ethyl 3α- and 3β-Methyl-9-oxobicyclo (3,3,1) nonane-1-carboxylates and Related Compounds
• Formation of 2-Acetyl-3-hydroxy-5-phenylmaleimide from Ethyl 3-Ethoxy-methylene-2,4-dioxovalerate and Phenylhydroxylamine
• 45 Tricyclo[3.3.0.0^]octan-3-one化合物を鍵中間体とするポリキナン型セスキテルペン類の合成研究 : (±)-Pentalenene及び(±)-Quadroneの全合成
• TOTAL SYNTHESIS OF (±)-PENTALENENE
• ジヒドロピリジノンを共通出発原料としたアルカロイド類の合成

もっと見る 閉じる

スポンサーリンク