78 8-Deoxyserratinine系lycopodium塩基の合成研究

スポンサーリンク

概要

• 論文の詳細を見る

• Lycopodium alkaloids, (±)-fawcettimine(1) and (±)-8-deoxyserratinine(3) were stereoselectively synthesized. The key intermediate (6) was stereoselectively prepared by two routes. The first route involved the Diels-Alder reaction of (10), obtained from (7) via (8) and (9), with butadiene. Acetalization of the adduct(11) gave (6). The second one consisted in conversion of the adduct(12) obtained from Diels-Alder reaction of (8) into (6) via (13). Dihydroxylation of (6), followed by oxidation with HIO_4, afforded the dialdehyde(15), which was successively treated with excess of morpholine-camphoric acid in Et_2O-HMPA, and (EtO)_2POCH_2CN to give regioselectively (18) and (19) in a 25:1 ratio. Selective hydrogenation of (18) on (Ph_3P)_3RhCl, followed by reduction with LiAlH_4 and treatment with N_3CO_2Bu^t gave (21), which was successively treated with Na-liq. NH_3, Jones' reagent, N-hydroxysuccinimide-DCC, CF_3CO_2H, and (n-Bu)_3N in CH_3CN to yield the lactam(28). Reduction of (28) with NaBH_4 gave the alcohols (30) and (31). Both (30) and (31) were transformed into the same ketone(34) via the same sequence of reactions; reduction with LiAlH_4, acylation with (CF_3CO)_2O-Py., selective hydrolysis with 0.2N KOH-MeOH, and Jones' oxidation. Epoxidation of (34) gave the epoxides (35) and (36). The epoxide(35) was successively treated with BF_3・Et_2O, Jones' reagent, H_2-Pd/C, and 1N KOH-MeOH to provide (±).-fawcettimine(1). The other epoxide(36) was converted into (±)-8-deoxyserratinine(3) by successive treatments with 1N KOH-MeOH, Jones' reagent, and NaBH_4.

• 天然有機化合物討論会の論文
• 1979-09-20

著者

• 高谷 宗男

  京都大学薬学部

• 原山 尚

  Faculty Of Pharmaceutical Sciences Kyoto University

• 犬伏 康夫

  京大薬学科

• 原山 尚

  京大薬

• 高谷 宗男

  京大薬

関連論文

• Total Synthesis of Chelerythrine, a Benzo[c]phenanthridine Alkaloid
• Total Synthesis of Lemaireocereine
• 22 フッ化セシウム存在下でのアリールプロパルギルエーテルのクライゼン転位 : 2-メチルアリールフランの生成とそのイソキノリンアルカロイド合成への応用(ポスター発表の部)
• CESIUM FLUORIDE-MEDIATED CLAISEN REARRANGEMENT OF ARYL PROPARGYL ETHER AND ITS APPLICATION TO THE SYNTHESIS OF CHELERYTHRINE
• Synthetic Studies on dl-Aspterric Acid, a Carotane-Type Sesquiterpene. II. Synthesis of dl-Aspterric Acid(Organic,Chemical)
• P-54 Arnottin IおよびArnottin II : 構造、合成、そのBenzo[c]phenanthridine Alkaloidとの生合成的関連性(ポスター発表の部)
• Concise Syntheses of the Oxo Derivatives of Benzo[c]phenanthridine Bases by N-Deformylated Cyclization Based on Vilsmeier-Haack Reaction
• 42 Macarpineの合成 : 異常Bischler-Napieralski反応によるAzoniaazulene骨格の形成(口頭発表の部)
• Synthetic Studies on Naturally Occurring Coumarins. II. Synthesis of 6,7-Dimethoxy- and 7,8-Dimethoxy-5-[(E)-3-oxo-1-butenyl]coumarins
• An Efficient Method for Preparing gem-Dimethylcyclopropanes from gem-Dibromocyclopropanes(Organic,Chemical)
• Reaction of 8,8-DibromobicycJo[5.1.0]octanes with Higher-Order Organocuprates(Organic,Chemical)
• AN EFFICIENT METHOD FOR PREPARING GEM-DIMETHYLCYCLOPLOPANES FROM GEM-DIBROMOCYCLOPROPANES
• スピロベチバン型セスキテルペンの形式合成
• CHEMILUMINESCENT REACTIONS OF "UNMODIFIED" FLAVINS
• Lycophlegmarineの合成研究(第1報)ピリジン-無水トリフルオロ酢酸-酸素によるエポキシ化およびFawcettimineの形式合成
• Alkoxycarbonylmethylation of(3R, 10bS)-3-Phenyl-2,3,5,6-tetrahydro-10bH-oxazolo[2,3-a]isoquinoline
• REVISION OF STRUCTURE OF A NEW COUMARIN ISOLATED FROM Artemisia carviforia Wall
• On the Repair of Thymine and Thymidine Bromohydrins : A Possible New Model for the Damage and Repair of Nucleic Acids
• 高次有機銅試薬を用いるgem-ジブロモシクロプロパン体のアルキル化反応について
• Convenient Synthesis of a Simple Coumarin from Salicylaldehyde and Wittig Reagent. II. : Synthesis of Bromo- and Methoxycarbonylcoumarins
• A Convenient Preparation of Salicylaldehydes from 2-Methylbenzofurans by Ozonolysis
• Synthetic Studies on Naturally Occurring Coumarins. I. A Convenient Synthesis of 5,8-Dimethoxy- and 7,8-Dimethoxycoumarins
• A CONVENIENT SYNTHESIS OF A SIMPLE COUMARIN
• Re-examination of the Synthesis of 7,8-Dimethoxy-2-methyl-3-(4', 5'-methylenedioxy-2'-vinylphenyl)iso carbostyril
• Concise Synthesis of dl-Febrifugine
• Re-revision of the Stereo Structure of Piperidine Lactone, an Intermediate in the Synthesis of Febrifugine
• Synthesis and Antimalarial Activity of Febrifugine Derivatives
• 4.Pilocereineの異性体Isopilocereineの構造について
• THE CHEMICAL REPAIR REACTION OF THYMINE AND THYMIDINE DIOL DERIVATIVES, MODELS OF OXIDATIVELY DAMAGED NUCLEIC ACIDS, BY TRIVALENT PHOSPHORUS COMPOUNDS
• Regioselective Intramolecular Aldol Condensation by Using Excess Morpholine-Camphoric Acid
• Total Syntheses of the Lycopodium Alkaloids (±)-Fawcettimine and (±)-8-Deoxyserratinine
• Synthetic Studies on 8-Deoxyserratinine Type Alkaloids. Selective Cyclization of the 1,2-Cyclohexanediacetaldehyde Derivative by Intramolecular Aldol Condensation
• 78 8-Deoxyserratinine系lycopodium塩基の合成研究
• The Stereochemistry of Diels-Alder Adduct of 2-(3-Acetoxypropyl)-5-methylcyclohex-2-en-1-one with Butadiene
• 60 2,5-DialkylcyclohexenoneのDiels-Alder反応を用いる2,3の天然物の合成研究
• チミジンリン酸エステルのブロムヒドリンのチミジンリン酸エステルへの変換について : チミジンヌクレオチドの酸化損傷体の修復に関するモデル反応
• 8 (±)-Cepharamineの合成
• 邦産ヒカゲノカズラ属植物の成分研究(第13報) : ミズスギ及びヤチスギランの成分について
• The Structures of Serratine and Serratanidine
• Structure of Serratanidine
• ONE-POT UNSYMMETRICAL DOUBLE SUBSTITUTION OF 8,8-DIBROMOBICYCLO[5.1.0]OCTANE AND ITS STEREOCEHMISTRY
• PHOTOCHEMISTRY OF 2-(3,4,5-TRIMETHOXYPHENYL)-4-(3,4-METHYLENEDIOXYPHENYL)-4-OXO-2-BUTENONITRILE (β-CYANOCHALCONE) : ANOMALOUS DIMERIZATION THROUGH ISOMERIZATION IN THE SOLID STATE
• AILANTHOIDINE, A NOVEL BENZO[C]PHENANTHRIDINE ALKALOID WITH A CYANOPYRIDINE PENDANT, FROM A XANTHOXYLUM SPECIES
• Stereo-Structures of Reaction Products of dl-1,3-Dimethylthymine Epoxide with Amines and L-Amino Acid Ethyl Esters(Organic,Chemical)
• Oxidation of Pyrimidine Base Derivatives with m-Chloroperbenzoic Acid
• OXIDATION OF 1,3-DIMETHYL DERIVATIVES OF PYRIMIDINE BASES WITH m-CHLOROPERBENZOIC ACID
• 41 ピクロトキサン型セスキテルペン,コリアミルチンの合成研究
• 24 (±)Hasubanonineの合成
• Synthesis of All-Methylated Isorugosin B
• Aryl-Aryl Coupling Reaction Using a Novel and Highly Active Palladium Reagent Prepared from Pd(OAc)_2, 1,3-Bis [diphenylphosphino] propane (DPPP), and Bu_3P
• One-Pot Conversion of Allyl Alcohols into Selenochroman Derivatives
• Synthesis of Arnottin I through a Palladium-Mediated Aryl-Aryl Coupling Reaction
• The Plane Structure of Serratinine
• Serratinine ; A Novel Skeletal Lycopodium Alkaloid
• 2 新しい骨格のリコポジウムアルカロイド : Serratinineの構造
• Synthesis and Antitumor Activity of Fused Quinoline Derivatives. V. Methylindolo[3,2-b]quinolines
• Synthese and Antifungal Activity of dl-Griseofulvin and Its Congeners. III
• Syntheses and Antifungal Activity of dl-Griseofulvin and Its Congeners. II
• INTERNAL ARYL-ARYL COUPLING REACTION USING A NOVEL AND HIGHLY ACTIVE PALLADIUM REAGENT PREPARED FROM Pd(OAc)_2,DPPP, and Bu_3P
• Regioselectivity in the Biaryl Coupling Reactions of 1-[(1,3-Benzodioxol-5-yl)methyl]-7-iodo-2,3-dihydroindole Using Palladium Reagent
• Concise Synthesis of Pyrrolophenanthridine Alkaloids Using a Pd-Catalyzed Biaryl Coupling Reaction with Regioselective C-H Activation
• Scandium(III) Trifluoromethanesulfonate Catalyzed Aromatic Nitration with Inorganic Nitrates and Acetic Anhydride
• Rare Earth Metal Trifluoromethanesulfonates Catalyzed Benzyl-Etherification
• Synthesis and Siderophore Activity of Vibrioferrin and One of Its Diastereomeric Isomers
• Total Synthesis of dl-Febrifugine and dl-Isoferifugine
• Total Synthesis of the Siderophore Vibrioferrin
• Direct Conversion of a Benzylic Hydroxy Group into a Selenenyl Group Using the Phenyl Trimethylsilyl Selenide-Aluminum Bromide Combination
• 1,3-ジメチルチミンエポキシドとアミン類との反応における溶媒効果(有機化学)
• 41 Serratene diol系triterpenoidのC-CH_3基帰属におけるNMR shift reagentの応用
• Construction of 1,3-Oxathiane Ring through Pummerer Reaction of γ, δ-Unsaturated Sulfinyl Compounds
• Convenient Transformation of Benzyl Alcohol into Its Corresponding Selenide Using the Selenolate Anion-Aluminum Chloride Combination System
• 邦産ヒカゲノカズラ属植物の成分研究(第7報) : ホソバトウゲシバとトウゲシバのアルカロイド成分
• 2 Serratinineと化学的に関連づけられる数種のLycopodium alkaloidの構造
• Total Synthesis of the Lycopodium Alkaloid dl-Serratinine
• The Stereochemistry of Diels-Alder Adduct of 5-Methyl-2-cyclohexene-1-one with Butadiene
• 24 リコポジウム塩基Serratinineの全合成
• Selective Cyclization of the 1,2-Cyclohexanediacetaldehyde Derivatives through the Intramolecular Aldol Condensation Reaction
• The Substituent Effect on the Addition Course of the Diels-Alder Reaction of 2-Methyl-5-substituted-1,4-benzoquinones with Butadiene
• The Structures of Two Lycopodium Alkaloids, Lycothunine and Lycophlegmarine, and the Configuration of the C_3-C_4 Bond of Fawcettimine and Fawcettidine
• Lycopodium Alkaloid, Serratanineの構造について
• 15 13-Acetyl-8-p-bromobenzoyl serratinineの結晶構造
• Synthesis of 7,8-Dimethoxy-N-methyl-2-phenyl-1,2,4,5-tetrahydro-3H-3-benzazepin-1-ol
• Serratinine誘導体の転位成績体の構造
• 4-Trimethylsiloxy-2H-thiopyranのEnophileとしての挙動について
• Structure of Serratinidine and Fawcettidine. A New Type of Lycopodium Alkaloid
• Stereochemistry and Biogenesis of Serratinine
• Isolation and Characterization of Alkaloids of the Chinese Drug "Chin-Shih-Hu."
• Total Synthesis of dl-Chamaecynone, a Termiticidal Norsesquiterpene
• The Revised Stereostructures of the Diels-Alder Adducts of l-Carvone with Butadiene
• カロタン型セスキテルペン,dl-アスプテリン酸の合成研究-1-dl-(3α,4ξ,6aα,10aα)-Octahydro-4-hydroxy-7,7-dimethyl-8H-3,10a-methano-1H-2-benzoxocin-8-oneの合成
• 第17回天然物化学談話会
• ヨウラクヒバのアルカロイド成分
• 目的意識を持って(薬学領域における基礎研究の意義とあり方)
• 第21回天然有機化合物討論会
• Structure of Serratine

もっと見る 閉じる

スポンサーリンク