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
スポンサーリンク
概要
- 論文の詳細を見る
Formal syntheses of (±)-catharanthine, one of the Iboga alkaloids, and (±)-tabersonine, one of the Aspidosperma alkaloids, were achieved from N-ethoxycarbonyl-1,6-dihydro-3(2H)-pyridinone (1a) as a common starting material. The key intermediate (7) for the Iboga alkaloids was prepared by two routes. The first route involved haloform reaction of 12, obtained from 2. The second one consisted of the Claisen rearrangement of 17, the precursor of 1a, and the subsequent hydroboration-oxidation. Ketalization of 7c and the subsequent PCC oxidation gave 42, which was converted to 50 via 49. Cyclization of 50 with p-TsOH afforded the pentacyclic ketone (51), which had already been transformed into (±)-catharanthine. On the other hand, 1a was treated with ethylmagnesium bromide to give the 1,2-adduct (54) along with the 1,4-adduct (55). Allylic rearrangement of the former, followed by the Claisen rearrangement, afforded 57, which was acetalized, hydrolyzed, and condensed with β-indolylacetyl chloride to give 60. The aldehyde (60) was smoothly oxidized with Ag_2O to yield 61, which then cyclized with PPA to (±)-5,16-dioxo-14,15-dehydroquebrachamine (53), the key intermediate for (±)-tabersonine. Thus, 1,6-dihydro-3(2H)-pyridinone system has been proved to be a potential synthon to some indole alkaloids.
- 天然有機化合物討論会の論文
- 1980-09-10
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