Studies on Indenopyridine Derivatives and Related Compounds. VI. : Synthesis adn Stereochemistry of Ethyl 9.9-Dimethyl-1,2,3,9a-tetrahydro-9H-indeno[2,1-b]pyridine-3-carboxylate as a Possible Intermediate for the Total Synthesis of Lysergic Acid

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概要

• 論文の詳細を見る

• Reaction of 1,1-dimethylindene-3-carbonyl chloride (9), prepared from 3,3-dimethylindanone (5) via a four step sequence, with ethyl 3-(N-tert-butoxycarbonyl-N-methyl)aminopropionate (14)or its 2-methyl derivative (15) in the presence of lithium diisopropylamide (LDA) gave the β-keto esters (16 and 17). De-tert-butoxycarbonylation of 16 followed by treatment with sodium bicarbonate did not give 12,while 17 afforded the cyclized β-keto ester (19) in good yield. Sodium borohydride reduction of 19 followed by treatment with methanesulfonyl chloride gave the mesylate (21), which was reacted with 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) to give the unsaturated ester (22). By analogous reaction sequences, the diethylamide derivative (2) was synthesized in moderate yield. Reaction of the β-keto ester (16) with diethyl phosphorochloridate in the presence of LDA gave the enolphosphate (30), which was converted to the unsaturated esters (31a and 31b) in good yields. However, dephosphorylation of 31 failed. Sodium borohydride reduction of 16 gave the alcohol (33), which was converted to the diene ester (34) or the mesylate (36). These were successfully converted to the ethyl 1,2,3,9a-tetrahydro-9H-indeno[2,1-b]pyridine-3-carboxylates (32s and 32b), which were found to exist in an equilibrium mixture, in excellent yields, respectively. The stereochemistry of some of the key intermediates and of the target compounds is discussed.

• 社団法人日本薬学会の論文
• 1986-07-25

著者

• 寺田 達也

  Osaka University Of Pharmaceutical Sciences

• 栗原 拓史

  Osaka University of Pharmaceutical Sciences

• 米田 龍司

  Osaka University of Pharmaceutical Sciences

• 里田 成代

  Osaka University of Pharmaceutical Sciences

• 栗原 拓史

  Osaka College Of Pharmacy

関連論文

• Synthetic Studies of (±)-Lysergic Acid and Related Compounds(Organic,Chemical)
• Studies on Indenopyridine Derivatives and Related Compounds. VI. : Synthesis adn Stereochemistry of Ethyl 9.9-Dimethyl-1,2,3,9a-tetrahydro-9H-indeno[2,1-b]pyridine-3-carboxylate as a Possible Intermediate for the Total Synthesis of Lysergic Acid
• A NEW SYNTHESIS OF (±)-LYSERGIC ACID
• Improved Synthesis of 5'-Deoxy-5'-adenosineacetic Acid
• Thermal Elimination of Carbonyl Sulfide from O-Aryl Thionocarbonates of Pyrrolidine-, Piperidine-, and Tetrahydrothiophene-2-ethanol
• Novel Transformation of Azabicyclothionocarbonate to Azaspirolactone
• Molecular Conformations of Aminophenylimidazoles Exhibiting Antiulcer Activities
• Studies on Ergot Alkaloids and Related Compounds. XIV. Syntheses of N-Alkyl-4-methyl-2,3,4,4a, 5,6-hexahydrobenzo [f] quinoline-2-carboxamides and Stereochemistry of Diethyl 4-Methyl-1-oxo-1,2,3,4,4a, 5,6,10b-octahydrobenzo [f] quinoline-2,2-dicarboxylate
• Studies on Ergot Alkaloids and Related Compounds. XIII. syntheses and Stereochemistries of 4-Methyl-1,2,3,-4,4a, 5,6,10b-octahydrobenzo[f]quinoline-2-carboxylic Acids
• Studies on 1,4-Benzothiazines. II. Acetylation of 2,3-Dihydro-3-imino-4H-1,4-benzothiazine
• Studies on 1,4-Benzothiazines. I. Synthesis of 2,3-Dihydro-3-imino-4H-1,4-benzothiazines and Acetylation of the N-Methyl Derivative
• Meisenheimer Rearrangement of Azetopyridoindoles. VII. Ring Expansion of 2-Phenylhexahydroazeto[1', 2' : 1,2]pyrido[3,4-b]indoles by Oxidation with m-Chloroperbenzoic Acid
• [3,3]Sigmatropic Ring Expansion of Cyclic Thionocarbonates. VII. On the Formation of 8-Membered Thionocarbonates as the Intermediates
• [3,3]Sigmatropic Ring Expansion of Cyclic Thionocarbonates. VI. Regioselective Wohl-Ziegler Bromination of 10-Membered Thiolcarbonates
• Chemistry of Tetrahydro-1,3-oxazin-2-one : New Method for the Synthesis of Indoloquinolizidine Derivatives
• MEISENHEIMER REARRANGEMENT OF 2-ETHENYL-1,4,5,10b-TETRAHYDRO-2H-AZETOPYRIDO[3,4-b__-]INDOLE N-OXIDES : NEW ROUTE TO THE 12(S)CARBA-EUDISTOMIN SKELETON
• Reductive Cyclization of o-Nitrobenzylideneacetylacetone Analogues
• Studies on Indenopyridine Derivatives and Related Compounds. III. Stereochemistry of 1-Substituted 4,9-Dihydroxy-9-phenyl-1,2,3,4,4a, 9a-hexahydro-9H-indeno [2,1-b] pyridines
• Reaction of Pyrazolo [1,5-α] pyrimidine Derivatives with Nucleophiles. V. X-Ray Determination of the Molecular Structure of a Reaction Product of 6,7-Diethoxycarbonylpyrazolo [1,5-α] pyrimidine-3-carbonitrile with N-Methylindole
• A New Method for the Preparation of 2-Hydroxymethyl-3-quinolinecarboxylic Acid Lactone Derivatives
• Reactions of Pyrazolo [1,5-α] pyrimidine Derivatives with Nucleophiles. IV. Some Reactions of 1,4-Dihydrocyclopent [b] indoles
• THE REACTION OF 1,4-DIHYDROCYCLOPENT [b] INDOLES WITH DIMETHYL ACETYLENEDICARBOXYLATE
• Reaction of 3-[3-(2-Nitrophenyl)-2-propenylidene]-2,4-pentanedione with Hydroxylamine Hydrochloride. Formation of a 2-Chloromethyleneindolin-3-one
• Reactions of Pyrazolo [1,5-a] pyrimidine Derivatives with Nucleophiles. III. Nucleophilic Addition to 6,7-Bis (ethoxycarbonyl) pyrazolo [1,5-a] pyrimidine-3-carbonitrile in the Presence of Triethyloxonium Fluoroborate
• Synthesis and Reactions of Ethyl 6-Acetyl-2,3-diphenylimidazo [1,2-a] pyrimidine-5-carboxylate and Related Compounds
• SYNTHESIS AND X-RAY CRYSTAL STRUCTURE DETERMINATION OF 1,4-DIHYDROCYCLOPENT [b] INDOLES
• Ring Transformations of 6H-Cyclopropa [e] pyrazolo [1,5-a] pyrimidine. III. Synthesis and X-Ray Crystal Structure Determination of a 1-Pyrazol-3-ylpyrrole-2-carboxylic Acid
• Reactions of Pyrazolo [1,5-α] pyrimidine Derivatives with Nucleophiles. I. Nucleophilic Addition to 6,7-Dicarbethoxypyrazolo [1,5-α]-pyrimidine-3-carbonitrile in the Presence of Boron Trifluoride Etherate
• Ring Transformations of 6H-Cyclopropa[5a, 6a]pyrazolo[1,5-a]pyrimidine. II. Reaction of 5a-Acetyl-6a-carbethoxy-5a, 6a-dihydro-6H-cyclopropa[5a, 6a]pyrazolo[1,5-a]pyrimidine-3-carbonitriles with N-Methylaniline
• Reactions of Ethyl 3-Ethoxymethylene-2,4-dioxovalerate and Ethyl Ethoxymethyleneoxaloacetate with Indole Analogs
• Studies on Ergot Alkaloids and Related Compounds. XII. Syntheses of Ethyl 4-Methyl-2,3,4,4α, 5,6-hexahydrobenzo[f]quinoline-2-carboxylate and its Dihydro Derivative
• Formation of 2-Acetyl-3-hydroxy-5-phenylmaleimide from Ethyl 3-Ethoxy-methylene-2,4-dioxovalerate and Phenylhydroxylamine
• Studies on Ergot Alkaloids and Related Compounds. XVI. On the So-called Bohlmann Absorption of 2,4-Disubstituted Octahydrobenzo [f] quinoline Derivatives
• Studies on Ergot Alkaloids and Related Compounds. XV. Reductions of cis- and trans-4-Methyl-2-methylen-3-oxo-1,2,3,4,4a, 5,6,10b-octahydrobenzo [f] quinolines and Preparation of trans-syn-2,4-Dimethyl-1,2,3,4,4a, 5,6,10b-octahydrobenzo-[f] quinoline
• REACTION OF METHYL VINYL KETONE CYANOHYDRIN PHOSPHATE WITH AROMATIC COMPOUNDS
• Meisenheimer Rearrangement of Azetopyridoindoles. V. Synthesis of 9-Methyl-12-carbaeudistomin and Related Compounds
• 1,4-and 1,7-Addition Reactions of 4-(Substituted benzylidene)-3,5-dimethylisopyrazoles
• Reaction of 4-(o-Nitrobenzylidene)-3,5-dimethylisopyrazole with Acyl Chlorides
• Studies on Indenopyridine Derivatives and Related Compounds. I. Syntheses and Stereochemistries of 1-Substituted 1,2,3,4,4a, 9a-Hexahydro-4-hydroxy-9H-indeno [2,1-b] pyridines and Related Compounds
• A NEW SYNTHESIS OF BIARYLS
• Meisenheimer Rearrangement of Azetopyridoindoles. III. Synthesis of 3,6-Epoxyhexahydroazocino[5,4-b]indoles
• Meisenheimer Rearrangement of Azetopyridoindoles. VI. Synthesis of 12-Carbaeudistomin and Related Compounds
• Application of Cyanophosphates in Organic Synthesis. Reactivity of α-Cyano-α-diethylphosphonooxy Anions(Organic,Chemical)
• Allylic Rearrangement of Cyanophosphates. III. : Reaction of Acyclic Enone Cyanophosphates
• Studies on Isopyrazole Derivatives and Related Compounds. I. Structure of Condensation Product of Nitrobenzylideneacetylacetone with Hydrazine Dihydrochloride
• [3,3]Sigmatropic Ring Expansion of Cyclic Thionocarbonates. IV. Relatioship between Ring Size of Cyclic Thionocarbonates and Geometry of Created Double Bond in Medium- and Large-Membered Thiolcarbonates
• Reductive Deoxygenation of α, β-Unsaturated Ketones via Cyanophosphates by Lithium in Liquid Ammonia
• Synthesis and Cycloaddition Reaction of 2-Cyano-3-indoleacetonitriles
• CYANOPHOSPHORYLATION OF KETONES AND ALDEHYDES USING DIETHYL PHOSPHOROCYANIDATE (DEPC)
• New Route to 1-(5-Imidazolyl)ribofuranoid Glycals from Ribofuranosyl Chloride and 5-Lithio-imidazole
• RECYCLISATION OF 2-OXOTETRAHYDRO-1,3-OXAZINES ACCOMPANIED BY DECARBOXYLATION : A CONVENIENT SYNTHESIS OF TETRAHYDROPYRIDINE, QUINOLIZIDINE, AND INDOLIZIDINE SKELETONS
• A New Synthesis of Allenic Nitriles from Ynones via Cyano Phosphates
• NEW ROUTE TO (Z)-ALLYLIC SULFIDES VIA A 10-MEMBERED THIOLCARBONATE
• Allylic Rearrangement of Cyanophosphate. II. Synthesis of β-Cyano-α, β-unsaturated Ketones
• ALLYLIC REARRANGEMENT OF α, β-UNSATURATED KETONE-DIETHYL PHOSPHOROCYANIDATE ADDUCTS

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