50(P10) Macrocarpal類の不斉合成研究(ポスター発表の部)

スポンサーリンク

概要

• 論文の詳細を見る

• Macrocarpals are structurally characterized by isopentyl phioroglucinol dialdehyde fused to various sesquiterpene skeletons, and are known to show several interesting biological activities such as antibacterial activity, inhibitory activity of HIV-RTase, aldose reductase, and glucosyltransferase. We describe herein the first stereoselective total synthesis of macrocarpal-C (3). Incidentally, we have revealed that 3 is identical with macrocarpal G (4), which was reported its planar structure only. As illustrated in our retrosynthetic analysis of macrocarpals (Scheme 2), we planned an efficient coupling of the aromatic side-chain unit with enone 8, prepared from commercially available and inexpensive (+)-3-carene (7). The ZnCl_2 mediated coupling reaction of the side-chain unit 20 with silyl dienol ether 21 gave the desired products 13 and 14 with no diastereoselectivity. However, we established the stereoselective approach for 13 or 14 by employing the chiral hexasubstituted benzene Cr(CO)_3 complexes (S- or R-22) as a benzyl cation equivalent. Having developed the stereoselective route to the promising precursor of macrocarpal-C 13, we investigated the following functional manipulations. Catalytic hydrogenation of the enone 13 afforded ketone 15 with proper stereochemistry. NaBH_4 reduction of the ketone in 15 followed by selective acetylation of the primary hydroxyl group led to monoacetate 28. After dehydration of the secondary hydroxyl group in 28 by modification of the Grieco's protocol, deacetylation gave primary alcohol 29 which was subjected to another dehydration furnishing exo-olefin 30. The next task was to convert the aromatic ring moiety of 30 into phioroglucinol dialdehyde. Ester reduction of 30 led to diol 31. Finally, 31 was subjected to TPAP oxidation followed by demethylation provided macrocarpal-C (3), which was identical with a natural authentic sample (^1H, and ^<13>C-NMR). Moreover, the synthetic sample was found to be identical with the natural macrocarpal G (4).

• 天然有機化合物討論会の論文
• 1997-07-20

著者

• 石田 寿昌

  大阪薬大

• 石田 寿昌

  大阪薬科大学

• 岩田 宙造

  阪大院薬

• 田中 徹明

  阪大院薬

• Tanaka T

  Kvushu Univ. Fukuoka Jpn

• 田中 徹明

  阪大薬

• 三神山 秀勲

  阪大薬

• 前田 公也

  阪大薬

• 岩田 宙造

  阪大薬

• Tanaka T

  Osaka Univ. Osaka Jpn

• 石田 寿晶

  大阪薬科大学

• 田中 恒雄

  Department Of Pharmacy Hyogo College Of Medicine

• Tanaka Tetsuaki

  Faculty Of Pharmaceutical Sciences Osaka University

関連論文

• 17 Theonella属海綿の産生する二量体マクロリド類の化学構造と抗腫瘍活性(口頭発表の部)
• 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 Aphidicolane and Stemodane Diterpenes. I. Synthesis of (2'R^*, 4a'S^*, 8a'R^*)-2', 8a'-Dimethyl-4a', 5', 8', 8a'-tetrahydrospiro [2,5-cyclohexadiene-1,1'(2H)-naphthalene]-3'(4'H), 4,6' (7'H)-trione
• 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
• イオノホア18員環ラクトンエポキシドGL2E4のX線結晶解析 : Ca2+イオン輸送能と結晶構造との相関(発表論文抄録(1996))
• テルペノイドの化学変換第X報 : ゲラニオールから合成した大環状ラクトンエポキシドのイオノホア活性(発表論文抄録(1994))
• Chemical Transformation of Terpenoids. X. Ionophoretic Activities of Macrocyclic Lactone Epoxides Synthesized from Geraniol
• テルペノイドの化学変換 第IX報 : E,E-Farnesolから合成した大環状ラクトンエポキシドのイオノホア活性(発表論文抄録(1993))
• Chemical Transformation of Terpenoids. IX. Ionophoretic Activities of Macrocyclic Lactone Epoxides Synthesized from E, E-Farnesol
• 102(P-59) (±)-Scopadulinの全合成(ポスター発表の部)
• 131(P-78) 抗腫瘍活性アセトゲニンMosin Bの不斉合成研究(ポスター発表の部)
• 多官能性化合物2- (N-シアノイミノ) チアゾリジン誘導体の合成化学的活用
• 50(P10) Macrocarpal類の不斉合成研究(ポスター発表の部)
• Synthetic Studies on Aphidicolane and Stemodane Diterpenes. V. A Facile Formal Total Synthesis of (±)-Aphidicolin via a Lewis Acid-Mediated Stereoselective Spiroannelation
• Lewis Acid-Mediated Stereoselective Spiroannelation : A Facile Access to Aphidicolane and Stemodane B/C/D Ring Systems
• P-18 (+)-Perhydrohistrionicotoxinの合成(ポスター発表の部)
• Synthetic Studies on Aromadendrane-Type Compounds. II.Stereoselective Synthesis of (+)-1,2-Didehydroaromadendrane
• Synthetic Studies on Aromadendrane-Type Compounds. I. Stereoselective Construction of Aromadendrane- and Alloaromadendrane-Type Skeletons
• Construction of Asymmetric Quaternary Carbon Center Containing Heteroatom via Regioselective Cleavage of Cyclopropane Ring Mediated by Mercury(II) Salt
• Synthetic Study on Gymnomitrol. II. A Synthesis of (±)-Isogymnomitrol
• 57 アロマデンドラン型化合物の不斉合成研究(ポスター発表の部)
• 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
• Efficient Chiral Induction by Diene Iron-Tricabonyl Moiety. IV. : Asymmetric Total Synthesis of a Piperidine Alkaloid, SS20846A
• Excellent Chiral Introduction by Diene Iron-Tricarbonyl Moiety. III : Asymmetric Synthesis of Hydroxyethylidene Dipeptide Isostere Using a Diastereoselective 1,2-Nucleophilic Addition of Organocerium Reagents into a 1-Azatriene Fe(CO)_3 Complex
• Excellent Chiral Introduction by Diene Iron-Tricarbonyl Moiety. II : A Formal Synthesis of (+)- and (-)-Frontalin Using a Diastereoselective 1,2-Nucleophilic Addition of Organometallics into a (Z)-Dienone Fe(CO)_3 Complex
• Effect of the Carbamoyl Group of Pyridine Coenzyme on the Interaction with Tryptophan : Crystallographic, Energy Calculation and Proton Nuclear Magnetic Resonance Studies Using Model Compounds(Physical,Chemical)
• On the Interaction between Flavin and Indole Rings. Crystallographic, Spectroscopic, Polarographic and Energy Calculational Studies of a Flavinyltryptamine Peptide
• Physicochemical Studies of Medicinal Drug Polymorphism. I. Structural Studies of Bromodiethylacetylurea by Thermal and X-Ray Crystal Analyses
• 93(P-22) 抗腫瘍活性アセトゲニン類の系統的不斉合成法の開発 : Murisolinの不斉合成への応用(ポスター発表の部)
• Soluble Expression of a Synthetic Gene for Human Translation Initiation Factor 4E in Escherichia coli
• Conformational Studies of N-2-(3-Indolyl)ethyl- and N-2-Phenylethyl-5'-deoxy-5'-adenosineacetamides by Spectroscopic and Energy Calculation Methods, as Model Compounds for Aminoacyladenylates
• 30 イネ科植物の根が分泌する金属キレーターに関する研究 : ムギネ酸の金属錯体の構造と性質
• ヒトeIF 4Eのジスルフィド結合に関する研究
• 沖縄産香辛料ヒハツモドキ Piper hancei の成分研究
• Structural Feature and Molecular Interaction of Basic Amino Acid-Picric Acid Complexes by X-Ray Crystal Analyses
• Binding Specificity of Mutagenic Tryptophan Pyrolysates for DNA Conformation : Spectroscopic and Viscometric Studies
• 蛋白質生合成開始因子-4Eの遺伝子発現とmRNAキャップ認識機構の研究
• Recognition of a Nucleic Acid Base by Tryptophan-Containing Peptides : Spectroscopic Comparison of the Interaction of Trp-Gly-Gly-Glu and Trp-Gly-Gly-Gln with 7-Methylguanine Base
• Molecular Conformation of Patellamide A, a Cytotoxic Cyclic Peptide from the Ascidian Lissoclinum patella, by X-Ray Crystal Analysis
• DEHATRINE, AN ANTIMALARIAL BISBENZYLISOQUINOLINE ALKALOID FROM THE INDONESIAN MEDICINAL PLANT BEILSCHMIEDIA MADANG, ISOLATED AS A MIXTURE OF TWO ROTATIONAL ISOMERS
• Conformational Features of 5'-O-[N-(L-Alanyl)sulfamoyl]adenosine, a Substrate Analogue of Alanyl-tRNA Synthetase, Studied by ^1H-NMR and Energy Calculation Methods
• X-Ray Crystal Structure of L-Tryptophan-Picric Acid Charge-Transfer Complex and Comparison with DL-Tryptophan-Picric Acid Complex
• Recognition of Nucleic Acid Base by Tryptophan-Containing Peptides : Spectroscopic Study on Interaction of N-AcetylTrp-(Gly)_m-Asp-(Gly)_n-TrpNHCH_3 (m=0-2,n=0-2) with Guanine Base
• Molecular Design of Potent Inhibitor Specific for Cathepsin B Based on the Tertiary Stucture Prediction
• Spectroscopic Study on Interaction of Nucleic Acid Base with Tryptophan-Containing Tripeptides : Acetyl-Trp-X-Trp-NHCH_3 (X=Gly, Asn, Asp, Gln and Glu)
• Sequence-Dependent Interaction of Acidic Amino Acid with Guanine Base in Tryptophan-Containing Dipeptides : Spectroscopic Studies
• Conformational Characteristics of Opioid κ-Receptor Agonist : Crystal Structure of (5S, 7S, 8S)-(-)-N-Methyl-N-[7-(1-pyrrolidinyl)-1-oxaspiro[4.5]dec-8-yl]benzeneacetamide (U69,593), and Conformational Comparison with Some κ-Agonists
• Molecular Conformations of Aminophenylimidazoles Exhibiting Antiulcer Activities
• エンケファリンの立体構造に基づくμ/δ-オピオイドレセプターの基質特異性
• Crystal and Molecular Structure of 6-Hydroxymelatonin : a Final Metabolite of Tryptophan
• Crystal Structure and Molecular Conformation of E-64,a Cysteine Protease Inhibitor
• Proton Nuclear Magnetic Resonance Study on the Aromatic Amino Acid-Guanine Nucleotide System : Effect of Base Methylation on the Stacking Interaction with Tyrosine and Phenylalanine
• Conformation Study of a Histamine H_2-Receptor Antagonist : Crystal Structures of 2-Acetoxy-N-[3-[m-(1-piperidinomethyl)-phenoxy]propyl]acetamide (Roxatidine Acetate) and Its Hydrochloride Salt
• トリプトファンの生体分子との相互作用に関する構造化学的研究
• A New Iridoid Glucoside, Nepetariaside, from Nepeta cataria(Organic,Chemical)
• Crystal Structure of (Uracil-1-ylethyl)(adenin-9-ylethyl)tryptophan Dipeptide: An Interaction Model between Nucleic Acid Base and Aromatic Amino Acid(Physical,Chemical)
• Crystal Structure of Copper(II) Complex with Tryptamine-Pyridoxal Schiff Base and Conformational Study of Tryptophan in Pyridoxal-Catalyzed Reactions
• A Stacking Interaction between Thymine and Phenyl Rings : Crystal Structure of 3'-O-Benzoylthymidine Monohydrate
• NEW ASPECTS OF THE 1,3-DIPOLAR CYCLOADDITION OF THIAZOLIUM N-IMINES WITH DIMETHYL ACETYLENEDICARBOXYLATE (DMAD)
• Studies on the Constituents of the Seeds of Hernandia ovigera L. IV. Syntheses of β-Peltatin-A and-B Methyl Ethers from Desoxypodophyllotoxin
• インドネシア薬用植物Beilschmiedia madangから回転異性体混合物として単離した抗マラリア活性ベンジルイソキノリンアルカロイド、デハットリン(発表論文抄録(1993))
• Platelet Anti-aggregant Activity of 2,2-Dimethylthiazolidine Hydrochloride and 2-(4-Hydroxy-3-methoxyphenyl)thiazolidine
• Synthetic Studies on Quadrone. I. An Approach to the Synthesis of (±)-Quadrone(Organic,Chemical)
• A FORMAL TOTAL SYNTHESIS OF (±)-QUADRONE
• Diastereoselective Synthesis of Optically Active C2-Substituted Spiro[4.5]decanes : Two Key Intermediates for Spirovetivane Sesquiterpenes
• P-53 ジエン鉄カルボニル錯体を不斉発現素子とし用いた不斉合成反応の開発および生理活性物質の不斉合成(ポスター発表の部)
• Asymmetric Desymmetrization of Prochiral 1,3-Diols via Diastereoselective C-O Bond Fission of Bicyclic Acetal Using a Chiral Sulfoxide as a Chiral Auxiliary
• スルフィニル基の特性を利用した新規合成反応の開発と天然物合成への応用
• 43 シダ植物成分 : マメヅタ属,イワヒトデ属植物に分布するonoceroidトリテルペン
• 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
• Synthetic Studies on Acorane-Alaskane Sesquiterpenes. II. : Total Synthesis of (±)-Acorenone
• Regioselective Functionalization of the Methylene Group Adjacent to Cyclopropyl Sulfide via Mercury(II)-Mediated Regioselective Ring-Opening Reaction
• 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-Asymmetric Induction by Reductive Acetal Cleavage of a Bicyclic Acetal Using a Sulfinyl Chiral Auxiliary
• 1,6-Asymmetric Induction Utilizing Asymmetric Desymmetrization by Diastereoselective C-O Bond Fission of the 4-Substituted Bicyclic Acetal : Application to a Synthesis of (-)-Frontalin
• 7,7-Dimethyltricyclo[3.3.0.0^]octan-3-ones as Synthetic Intermediates. III. : Total Synthesis of (±)-Descarboxyquadrone
• チオールプロテアーゼ阻害剤, E-64-C, のパパインとの結合樣式とその多樣性
• 生理活性物質のコンフォメーションと活性の相関
• ベルリン自由大学結晶学研究所滞在記
• Studies on Novel and Chiral 1,4-Dihydropyridines. I. Synthesis and Conformational Analysis of Novel NADH Model Compounds, N-Substituted (S)-3-(p-Tolylsulfinyl)-1,4-dihydropyridines
• Syntheses of Optically Active 1,4-Dihydropyridines Having a p-Tolylsulfinyl Group and Their Applications
• マムシ毒由来ホスホリパーゼA2の構造解析
• 沖縄産香辛料ヒハツモドキPiper hanceiの成分研究
• ペプチド及びDNAラセミ結晶における構造と天然型との類似性
• 生体分子の立体構造と分子間相互作用の研究を振り返って
• 分子識別能を有するトリプトファンの構造に魅せられて
• トリプトファンとピリジン,フラビンおよびチアミン補酵素との芳香環相互作用の構造化学
• P-22 Streptomyces属放線菌の生産する新規ポリケタイドalchivemycin類の構造(ポスター発表の部)

もっと見る 閉じる

スポンサーリンク