P-43 16員環マクロリド・ヒグロリド類の全合成研究(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
Hygrolidin (1), isolated from Streptomyces hygroscopicus in 1982, is a member of a family of structurally related macrolide antibiotics, which include other hygrolidins, the bafilomycins, and the concanamycins. These macrolides characterized by the diene lactone rings have recently been demonstrated to be a potent and specific ATPase inhibitor. The unique biological profile coupled with their novel molecular architecture has elicited considerable attention from synthetic chemists. We report herein the synthetic studies on hygrolidin (1), in which one of the key features is the conformational analysis with NMR technique and molecular mechanics calculations. Hygrolidin (1) was retrosynthetically disconnected to three fragments, C1-C12 fragment 9, C13-C17 fragment 8, and C18-C25 fragment 7. The fragment 9 was prepared from methyl (S)-3-hydroxy-2-methylpropionate using the Roush's crotylboron addition, carbometalation with Cp_2ZrCl_2-Me_3Al, and Horner-Emmons reaction. The fragments 7 and 8 were synthesized by exploiting the Evans' aldol reaction as a key reaction. The aldol coupling of 8 and 9 was accomplished with the aid of LiHMDS-ZnCl_2, followed by transformation of the adduct into the seco acid derivative 30. As might be anticipated from the molecular mechanics calculation using CONFLEX3, the macrolactonization of 30 proceeded smoothly under the modified Yamaguchi's conditions to give the desired macrolactone 31 in a good yield. The final aldol coupling of C1-C17 fragment 32 and C18-C25 fagment 7 is currently under investigation, in which we have obtained the aldol adduct 33 according to the Evans' protocol with PhBCl_2-^iPr_2NEt, albeit in a low yield.
- 天然有機化合物討論会の論文
- 1995-09-01
著者
関連論文
- 30 カルシウムチャネル活性化物質ピンナトキシンAの全合成(口頭発表の部)
- 71(P52) ザラゴジン酸類の合成研究(ポスター発表の部)
- P-74 ピンナトキシンAの全合成研究(ポスター発表の部)
- P-64 含リン脱離基法を用いるO18抗原の合成研究(ポスター発表の部)
- P-45 カルボニルイリドの1,3-双極付加環化反応を機軸とするポリガロリド類の全合成研究(ポスター発表の部)
- ザラゴジン酸の全合成:ロジウム(II)触媒を用いる骨格形成反応 (最新有機合成化学--ヘテロ原子・遷移金属化合物を用いる合成) -- (第3部 天然物合成)
- 奨励賞受賞 中村精一氏の業績
- 12 スクアレン合成酵素阻害物質ザラゴジン酸類の第二世代合成(口頭発表の部)
- 97(P-42) ピンナトキシンAの合成研究(ポスター発表の部)
- 薬学会賞受賞 北 泰行氏の業績
- 金属カルベン中間体を経るイリド形成を機軸とする不斉触媒反応
- ロジウム(II)錯体を用いる不斉触媒反応
- Double Stereodifferentiation in Intramolecular C-H Insertion Reaction toward the Synthesis of 1β-Methylcarbapenem Antibiotics
- ロジウム(II)錯体触媒を用いる不斉C-H挿入反応 (生物活性天然物の合成--複雑な構造をいかにして構築するか) -- (骨格構築法)
- 奨励賞受賞 中島 誠氏の業績
- タキソ-ルと同一の作用機序をもつ抗がん活性抗生物質エポチロンの全合成 (1997年の化学-7-)
- オリゴ糖鎖合成の新戦略
- AN EXTREMELY MILD AND GENERAL METHOD FOR THE CONSTRUCTION OF 1,2-TRANS-β-GLYCOSIDIC LINKAGES VIA GLYCOPYRANOSYL DIETHYL PHOSPHITES WITH PARTICIPATING GROUPS AT C-2
- P-43 16員環マクロリド・ヒグロリド類の全合成研究(ポスター発表の部)
- 含リン脱離基を基盤とする高選択的グリコシル化反応
- プロスタグランジンの合成と医薬 (脂質の化学と生化学) -- (脂質の生化学)
- グリコシル化反応の新展開
- AN EFFICIENT CONSTRUCTION OF 1,2-TRANS-β-GLYCOSIDIC LINKAGES VIA BENZYL-PROTECTED GLYCOPYRANOSYL P, P-DIPHENYL-N-(p-TOLUENESULFONYL)-PHOSPHINIMIDATES
- 現代化学増刊3 有機合成の最前線-高選択性を追及する-, 向山光昭, 土橋源一編, B5判, 252頁, 3800円(東京化学同人)
- 総合有機化学実験 I, II, S.ヒューニッヒ, G.メルクル, J.ザウワー著, 吉村嘉次, 野村祐次郎, 中川淑郎, 橋本弘信訳, A5判/1360頁, II360頁/各2,800円, (森北出版)
- 市販の不斉試薬
- コリスミン酸からプレフェン酸へのClaisen転位はいす型遷移状態を経る
- Catalytic asymmetric synthesis of descurainin via 1,3-dipolar cycloaddition of a carbonyl ylide using Rh2(R-TCPTTL)4
- A Stereoselective Total Synthesis of (9S)-9-Dihydroerythronolide A via Coupling between the Right-Half (C1-C6) Aldehyde and the Left-Half (C7-C15) Sulfoxide
- Synthetic Study of (9S)-9-Dihydroerythronolide A via Witting-Horner Coupling of C1-C6 and C7-C15 Segments
- Alternative Syntheses of the C9-C15 and C1-C5 Segments of Erythronolide A via Regio- and Stereo-Selective Reductive Ring Opening of 2,3-Epoxy Alcohols
- 3-METHOXYBENZYL (3-MPM) ABD 3,5-DIMETHOXYBENZYL (3,5-DMPM) PROTECTING GROUPS FOR THE HYDROXY FUNCTION LESS READILY REMOVABLE THAN 4-METHOXYBENZYL (MPM)AND 3,4-DIMETHOXYBENZYL (DMPM) PROTECTING GROUPS BY DDQ OXIDATION
- Enantioselective amination of silylketene acetals with (N-arylsulfonylimino)phenyliodinanes catalyzed by chiral dirhodium(II) carboxylates: asymmetric synthesis of phenylglycine derivatives
- Catalytic Enantioselective Aziridination of Alkenes Using Chiral Dirhodium(II) Carboxylates
- Dirhodium(II) tetrakis(perfluorobutyrate)-catalyzed 1,4-hydrosilylation of α,β-unsaturated carbonyl compounds
- P-26 CATALYTIC ENANTIOSELECTIVE SYNTHESIS OF (-)-METAZOCINE
- 92(P08) 光学活性(-)-フペルジンAおよびその含フッ素類縁体の合成研究(ポスター発表の部)
- P-16 ENANTIOSELECTIVE SYNTHESIS OF TETRAHYDROPYRAN NATURAL PRODUCTS EXPLOITING DIRHODIUM (II)-CATALYZED HETERO-DIELS-ALDER REACTION
- Asymmetric syntheses of diarylheptanoid natural products (−)-centrolobine and (−)-de-O-methylcentrolobine via hetero-Diels–Alder reaction catalyzed by dirhodium(II) tetrakis[(R)-3-(benzene-fused-phthalimido)-2-piperidinonate]
- Catalytic asymmetric hetero-Diels–Alder route to a key intermediate for the synthesis of calyxin L
- Enantioselective Synthesis of 3-Arylindan-1-ones via Intramolecular C-H Insertion Reactions of α-Diazo-β-Ketoesters Catalyzed by Chiral Dirhodium(II) Carboxylates
- Dirhodium(II) Tetrakis[N-benzene-fused Phthaloyl-(S)-piperidinonate] as a Chiral Lewis Acid: Catalytic Enantioselective Aldol Reactions of Acetate-derived Silylketene Acetals and Aldehydes
- Highly Enantio- and Diastereoselective Construction of 1,2-Disubstituted Cyclopentane Compounds by Dirhodium(II) Tetrakis[N-phthaloyl-(S)-tert-leucinate]-Catalyzed C–H Insertion Reactions of α-Diazo Esters
- Practical Synthesis of Dirhodium (II) Tetrakis[N-phthaloyl-(S)-tert-leucinate]
- P-46 海洋産ポリエーテルマクロリド、ハリコンドリンBの全合成研究(ポスター発表の部)
- Large Laboratory Scale Synthesis of (2S, 3S)-2-(4-Methoxybenzyloxy)-3,4-O-(3-pentylidene)-1,3,4-butantriol, a Versatile Chiral Building Block in Natural Product Synthesis
- Stereoselective Synthesis of Optically Active 4-Ethyl-3,5-dihydroxy-2-methylpentyl Derivatives. A Basic Building Block with Three Contiguous Chiral Centers of Polyether Antibiotics
- 24 海洋産ポリエーテルマクロリド、ハリコンドリンBの全合成研究(口頭発表の部)
- 光学活性な天然ホスト分子としてのポリエーテル抗生物質
- Sythesis of Erythronolide A via Direct Macrolactonization of a Conformationally Controlled Seco-acid with the Yamaguchi Reagent in the Presence of Dimethylaminopyridine
- 25 ポリエーテル抗生物質リソセリンの立体選択的全合成(口頭発表の部)
- 41 14員環マクロリドのセコ酸誘導体の立体配座計算とマクロラクトン化(口頭発表の部)
- 51 高立体選択的ヘテロジールスアルダー反応の開発とポリアミン系アルカロイドカンナビサチビンの合成への応用(口頭発表の部)
- Highly Stereocontrolled Total Synthesis of the Polyether Antibiotic Salinomycin. IV. Chemical Degradation of Salinomycin for the Structure Confirmation of Synthesic Key Intermediates
- Highly Stereocontrolled Total Synthesis of the Polyether Antibiotic Salinomycin. III. Total Synthesis of Salinomycin via Coupling of C1-C9,C10-C17,and C18-C30 Segments
- Highly Stereocontrolled Total Synthesis of the Polyether Antibiotic Salinomycin. II. Synthesis of Right (C18-C30) Segments from D-Glucose, D-Mannitol, and Ethyl L-Lactate
- Highly Stereocontrolled Total Synthesis of the Polyether Antibiotic Salinomycin. I. Synthesis of the Left (C1-C9) and Middle (C10-C17) Segments from D-Glucose
- 69 エリスロノリドAの改良合成(口頭発表の部)
- 62(PA2-2) ポリエーテル系抗生物質イソラサロシドAとラサロシドAの合成研究(ポスター発表の部)
- 71 イオノフォアポリエーテル抗生物質リリノマイシンの立体選択的合成
- Stereoselective Total Synthesis of 16-Membered Macrolide Aglycons, Leuconolides and Maridonolides. Macrocylic Stereocontrol Based on Conformational Analysis of the 16-Membered Macrolide Ring
- チタノセン触媒を用いた不斉還元反応
- カルシウムチャネル活性化物質ピンナトキシンAの全合成
- Enantioselective Intramolecular C-H Amidation of Sulfamate Esters Catalyzed by Chiral Dirhodium(II) Carboxylates
- 31 環上での立体制御反応を利用した16員環マクロリド類の合成(口頭発表の部)
- グリコシルジフェニルホスファートを用いる1,2-cis-α-グリコシド結合の立体選択的構築とα-ガラクトシルセラミド(KRN7000)の合成
- 113(P-42) 抗腫瘍活性18員環マクロリド・テダノリドの全合成研究(ポスター発表の部)
- Synthesis of Macrocyclic Amides. Formation of a New Symmetric 36-Membered Tetramide Ring
- Facile Total Synthesis of Carbonolides by Witting-Hoener Macro-Cyclization and Stereoselective Epoxidation
- マクロリド合成
- Highly Stereoselective Total Synthesis of Pikronolide, the Aglycon of the First Macrolide Antibiotic Pikroraycin. Crucial Role of Benzyl-Type Protecting Groups Removable by 2,4-Dichloro-5,6-dicyanobenzoquinone Oxidation(Organic,Chemical)
- Highly Stereoselective Total Synthesis of Methynolide, the Aglycon of the 12-Membered Macrolide Antibiotic Methymycin. III. An Efficient Synthesis of Methynolide(Organic,Chemical)
- 43 Wittig-Horner反応による閉環をキーステップとするマクロリド抗生物質の合成 : メチノリド・ピクロノリド・タイロノリドの高立体選択的合成
- 金属カルベン中間体を経るイリド形成を機軸とする不斉触媒反応
- オリゴ糖鎖の合成を志向したグリコシル化反応の開発
- 112(P48) 紅藻由来の環状ポリケタイド化合物の合成研究(ポスター発表の部)
- 研究の継続性と独自性
- 学術貢献賞受賞 高畑廣紀氏の業績
- P-67 カルボニルイリドの不斉1,3-双極付加環化反応を機軸とするコプシロシン Aの合成研究(ポスター発表の部)
- P-3 カルボニルイリドの1,3-双極付加環化反応を機軸とするオキサビシクロ骨格を有する天然物の触媒的不斉合成(ポスター発表の部)