Studies on the development of new, short, and practical synthetic methods for the synthesis of isocarbacyclin
异卡巴环素合成新、短、实用的合成方法开发研究
基本信息
- 批准号:05453129
- 负责人:
- 金额:$ 4.74万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for General Scientific Research (B)
- 财政年份:1993
- 资助国家:日本
- 起止时间:1993 至 1995
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
This research has established a novel, short-step, convergent, and practical method for the synthesis of isocarbacyclin featuring a one-pot, three-step process involving vinyl ether formation, Claisen rearrangement, and en reaction to give bicyclo [3.3.1]-backbone, which is not relying on any previous idea in this field that is principally the same as that for prostaglandin synthesis. The new method provided in this research can construct cyclopentenone framework bearing the homoallylic omega-chain longer by one-carbon at first followed by the introduction of the alpha-chain shorter by two-carbon to furnish the precursor for the bicyclo [3.3.1]-backbone. The method required (4S)-4-(O-tert-butyldimethylsilyl)-cyclopent-2-en-1-one as an important starting chiral compound, the antipode of which has been well-known starting material in PG synthesis. In other words, therefore, (4S)-isomer is given significant value which has not been experienced so far.A chiral synthon corresponding to the homoallylic omega-chain has been synthesized efficiently from (S)-1,2-(O-isopropylidene) glycerol in twenty-gram scale and 80-95% yield for each step through a series of routine reactions (7 steps).A precursor for the bicyclo [3.3.1]-backbone to be submitted to the one-pot, three-step process can be provided from an allylic tert-alcohol by vinyl ether formation. We hoped that a reaction to be used in this transformation should be free from mercury salts for some reasons and, after several attempts, has succeeded in developing a new, general method for the synthesis of vinyl ether from various allylic alcohols including tert-versions.
本研究建立了一种新颖、短步、收敛且实用的异碳环素合成方法,该方法包括乙烯醚形成、Claisen重排和en反应生成双环的一锅三步过程[3.3.1] -backbone,它不依赖于该领域任何先前的想法,基本上与前列腺素合成相同。本研究提供的新方法可以首先构建带有长一个碳的同烯丙基omega链的环戊烯酮骨架,然后引入短两个碳的α链,以提供双环的前体[3.3.1] -骨干。该方法需要(4S)-4-(O-叔丁基二甲基甲硅烷基)-环戊-2-en-1-酮作为重要的起始手性化合物,其对映体是PG合成中众所周知的起始原料。换句话说,因此,(4S)-异构体被赋予了迄今为止从未经历过的重要价值。由(S)-1,2-(O-异亚丙基)有效合成了对应于同烯丙基欧米伽链的手性合成子) 甘油以 20 克规模,通过一系列常规反应(7 个步骤),每一步的产率为 80-95%。双环 [3.3.1]-主链的前体将提交给可由烯丙基叔醇通过形成乙烯基醚来提供一锅三步法。由于某些原因,我们希望用于该转化的反应应不含汞盐,经过多次尝试,我们已成功开发出一种新的通用方法,用于从各种烯丙醇(包括叔烯丙醇)合成乙烯基醚。
项目成果
期刊论文数量(22)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Tadakatsu Mandai, Shin-ichi Matsumoto, Makoto Kohama, Mikio Kawaada, Jiro Tsuji, Seiki Saito, Toshio Moriwake: "A New Highly Efficient Synthetic Method for Isocarbacyclin Based on the Tandem Claisen Rearrangement and Ena Reaction" J.Org.Chem.55. 5671-5673
Tadakatsu Mandai、Shin-ichi Matsumoto、Makoto Kohama、Mikio Kawaada、Jiro Tsuji、Seiki Saito、Toshio Moriwake:“基于串联 Claisen 重排和 Ena 反应的异卡巴环素新型高效合成方法”J.Org.Chem.55。
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- 影响因子:0
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Tadakatsu Mandai, Jiro Tsuji, Yoshikazu Tsujiguchi, Seiki Saito: "A Novel Route to Cross-Conjugated 4-Oxo-5-alkylidene-2-cyclopentanecarboxylates by Pd (0)-Catalyzed Vicinal Carbonylation of 4-En-2-ynyl Carbonates" J.Am.Chem.Soc.115. 5865-5866 (1993)
Tadakatsu Mandai、Jiro Tsuji、Yoshikazu Tsujiguchi、Seiki Saito:“通过 Pd (0) 催化 4-En-2-ynyl 碳酸酯的邻位羰基化形成交叉共轭 4-Oxo-5-亚烷基-2-环戊烷甲酸酯的新路线”
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Tadakatsu Mandai and Seiki Saito: "A Novel Route to Cross-Conjugated 4-Oxo-5-alkylidene-2-cyclopentenecarboxylates by Pd(0)-Catalyzed Vicinal Carbonylation of 4-En-2-ynyl Carbonates" The Journal of the American Chemical Society. 115. 5865-5866 (1993)
Tadakatsu Mandai 和 Seiki Saito:“通过 Pd(0) 催化 4-En-2-ynyl 碳酸酯的邻位羰基化形成交叉共轭 4-Oxo-5-alkidene-2-cyclopentenecarboxylates 的新路线” 美国化学杂志
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Seiki Saito, Tetsuya Hara, Kazuhito Naka, Tetsushi Hayashi, Toshio Moriwake: "Enantioselective synthesis of Fundtionalized Cyclopentenone and Alkylidenecyclopentane Derivatives from Acyclic Bisallylic Diol Framework" Synlett. 241-242 (1992)
Seiki Saito、Tetsuya Hara、Kazuhito Naka、Tetsushi Hayashi、Toshio Moriwake:“从无环双烯丙基二醇框架中对映选择性合成基础环戊烯酮和亚烷基环戊烷衍生物”Synlett。
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Tadakatsu Mandai, Masaki Ueda, Shun-ichi Hasegawa, Mikio Kawada, Jiro Tsuji, Seiki Saito: "Prparation and Rearrangement of2-Allyloxyethyl Aryl Sulfoxides ; A Mercury-free Claisen Sequence" Tetrahedron Lett.31. 4041-4044 (1990)
Tadakatsu Mandai、Masaki Ueda、Shun-ichi Hasekawa、Mikio Kawada、Jiro Tsuji、Seiki Saito:“2-烯丙氧基乙基芳基亚砜的制备和重排;无汞克莱森序列”四面体 Lett.31。
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SAITO Seiki其他文献
Development of a Molecular Dynamics Method with Heat Transfer into Bulk for Ion Injection into Materials
开发一种将离子注入材料的传热到本体的分子动力学方法
- DOI:
10.1585/pfr.15.2403073 - 发表时间:
2020 - 期刊:
- 影响因子:0.8
- 作者:
SAITO Seiki;NAKAMURA Hiroaki;SAWADA Keiji;KOBAYASHI Masahiro;GAKUSHI Kawamura;MASAHIRO Hasuo - 通讯作者:
MASAHIRO Hasuo
SAITO Seiki的其他文献
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{{ truncateString('SAITO Seiki', 18)}}的其他基金
Novel Domino Cross-aldol/Tishchenko Reaction Promoted by NaH
NaH 促进的新型多米诺交叉羟醛/Tishchenko 反应
- 批准号:
13450373 - 财政年份:2001
- 资助金额:
$ 4.74万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Novel aromatization reaction of enamines employing Pd (II) complex
使用 Pd (II) 配合物的烯胺新型芳构化反应
- 批准号:
10450342 - 财政年份:1998
- 资助金额:
$ 4.74万 - 项目类别:
Grant-in-Aid for Scientific Research (B).
Development of practical methods for the synthesis of taxane diterpenoids
紫杉烷二萜合成实用方法的开发
- 批准号:
09555286 - 财政年份:1997
- 资助金额:
$ 4.74万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Development of novel carbon-nitrogen bond forming reactions by means of [2,3] sigmatropic rearrangement
通过[2,3]σ重排开发新型碳氮键形成反应
- 批准号:
08455430 - 财政年份:1996
- 资助金额:
$ 4.74万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Studies on the development of new, practical synthetic methods for the synthesis of physiologically active compounds related to vitamin D
研究开发新的、实用的合成方法来合成与维生素D相关的生理活性化合物
- 批准号:
06555281 - 财政年份:1994
- 资助金额:
$ 4.74万 - 项目类别:
Grant-in-Aid for Scientific Research (A)
Development of Highly Versatile C_4-Chiral Building Blocks from L-Malic acid and Their Utilization in Natural Product Syntheses
L-苹果酸高度通用的 C_4-手性结构单元的开发及其在天然产物合成中的应用
- 批准号:
60550613 - 财政年份:1985
- 资助金额:
$ 4.74万 - 项目类别:
Grant-in-Aid for General Scientific Research (C)