37(D-7) ブレベトキシンBの合成研究(口頭発表の部)
スポンサーリンク
概要
- 論文の詳細を見る
Brevetoxin B (1), a potent neurotoxin was isolated from the red tide organism Gymnodinium breve Davis in 1981. The unique structural features and biological activity of this molecule have attracted the attention of synthetic chemists. We have already reported the efficient method for the convergent synthesis of polycyclic ethers via the intramolecular allylation and subsequent ring-closing metathesis. Herein we report the convergent synthesis of the polycyclic framework of 1 based on our own methodology. The reaction of the bicyclic compound 12, prepared from the known compound 9, with the allylic silane 13 in the presence of TMSOTf gave the desired product 14, stereoselectively. The JK ring segment 6 was synthesized in 11 steps including one-carbon elongation from 14. Palladium-catalyzed coupling of the ketene acetal triflate 22, prepared from the known compound 18, and the organozinc reagent 23 gave the enol ether 24, which was converted to the BC ring segment 7. The connection of 7 and the FG ring segment 8 followed by several transformations afforded the allylic stannane 29. The partial reduction of 29 with DIBALH followed by trapping of the resulting aluminum hemiacetal with acetic anhydride provided the acetoxy ether 30. However, the yield was very low. Alternatively, the chlorosulfide 31, prepared from 26, was treated with the alcohol 8 in the presence of AgOTf to provide the O,S-acetal 32. Cyclization of 33 using AgOTf as a Lewis acid gave the desired product 34, stereoselectively. The construction of the E ring and the A ring via ring-closing metathesis afforded the ABCDEFG ring segment 5. The alcohol 5 and the carboxylic acid 6 were connected successfully by Yamaguchi conditions to give the ester 41. The construction of the polycyclic framework of 1 was performed via the intramolecular allylation and subsequent ring-closing metathesis to yield 46. Completion of the total synthesis of 1 is currently under way.
- 2004-10-01
著者
関連論文
- 26 ガンビ***ールの合成研究(口頭発表の部)
- 41 ポリ環状エーテルの収束的合成とガンビ***ール全合成への応用(口頭発表の部)
- 1P171 Oxygen binding properties of hemoglobins from diving mammals(5. Heme protein,Poster Session,Abstract,Meeting Program of EABS & BSJ 2006)
- Influence of a Single Amide Group on the Redox Function of Pseudomonas aeruginosa Cytochrome c_
- ブレベトキシンBの全合成
- P-31 ブレベトキシンBの全合成(ポスター発表の部)
- 37(D-7) ブレベトキシンBの合成研究(口頭発表の部)
- 119(P62) ポリ環状エーテルの立体選択的合成とその応用(ポスター発表の部)
- Characterization of Non-Native Heme Coordination Structures Emerging upon Guanidine Hydrochloric Acid-Induced Unfolding of Pseudomonas aeruginosa Ferricytochrome c_
- ホウ素元素を導入した新しい酵素阻害剤の開発に関する研究 (平成14年度専門研究会報告書「中性子捕捉療法システムの高度化」)
- π-アリルパラジウム錯体を用いる有機合成のルネッサンス
- 99 中性子捕捉療法による癌治療のためのホウ素キャリアーの設計と合成(ポスター発表の部)
- Inclusion Complexation of 4-Biphenylcarboxylate, 4-Biphenylacetate, and 4-Biphenylsulfonate with α-Cyclodextrin, Studied by Pulse Radiolysis
- Determination of Association Constants for Cyclodextrin Inclusion Complexation by Pulse Radiolysis
- ^FNMR Study on the Heme Electronic Structure in Oxy and Carbonmonoxy Reconstituted Myoglobins
- ^FNMR Study of the Heme Orientation and Electronic Structure in a Myoglobin Reconstituted with a Ring-Fluorinated Heme
- 11 14族有機金属化合物を用いる新規環化反応の開発とポリエーテル系天然物合成への応用(口頭発表の部)
- 38 Gambierolの合成研究(口頭発表の部)
- Reduction-Alkylation with Organocopper(I) Reagents-Alkyl Halides : Highly Regioselective α-Alkylation of γ-Acetoxy-α, β-enoates with Lithium Dibutylcuprate-Alkyl Halides and Difference in the Reactivity of Electron-Deficient Olefins with Organocopper(I)-L
- Characterization of the acid-alkaline transition in the individual subunits of human adult and foetal methaemoglobins
- Heme Is Not Required for Aquifex aeolicus Cytochrome c_ Polypeptide Folding
- Correlation between the Stability and Redox Potential of Three Homologous Cytochromes c from Two Thermophiles and One Mesophile
- Lewis Acid-Catalyzed Hydrometalation and Carbometalation of Unactivated Alkynes
- 有機銅-ルイス酸複合剤の最近の展開
- 海洋産ポリ環状エーテル, シガトキシン類の合成研究
- 全合成 (特集 21世紀の化学--残された大テ-マ 逆説"The End of Chemistry")
- 有機金属ルイス酸複合系
- アリルスズの分子内反応を用いるポリ環状エーテルおよび関連ヘテロ環化合物の立体選択的合成
- 24 ヘミブレベトキシンBの全合成(口頭発表の部)
- 有機銅を用いた不斉誘起反応
- Determination of Oxygen Binding Properties of the Individual Subunits of Intact Human Adult Hemoglobin
- Field-dependent ^F NMR study of sperm whale myoglobin reconstituted with a ring-fluorinated heme
- 38 ブレベナールの全合成(口頭発表の部)