Novel Tandem Desulfurization and Hydroxylation in Aqueous Media (Towards the Asymmetric Synthesis of New and Effective Anti-cancer Agents)

水介质中的新型串联脱硫和羟基化(致力于新型有效抗癌剂的不对称合成)

基本信息

  • 批准号:
    15550031
  • 负责人:
  • 金额:
    $ 2.43万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
  • 财政年份:
    2003
  • 资助国家:
    日本
  • 起止时间:
    2003 至 2004
  • 项目状态:
    已结题

项目摘要

Recent disclosures from this laboratory have demonstrated SmI_2-promoted tandem desulfurization and high erythro-selective coupling reactions of aromatic lactams with carbonyl compounds. Although significant progress, thus, has been made in advancing the versatility of sulfur-substituted lactams, the lack of studies concerning the reactivity toward simple Lewis acids is surprising except the lactol type of compounds. Herein we wish to report our successful efforts for the development of novel Lewis acid-mediated tandem reaction of phenylthio-substituted alicyclic and aromatic lactams in aqueous media, leading to the γ-hydroxylated products, whose process was further applied to the convenient total synthesis of isoindolobenzazepine natural product, chilenine.Whereas the reactions with FeCl_3 and CuI gave the desired γ-hydroxylated product, but in low yield, respectively, use of CuCl or CuBr had a dramatic effect on the rate and smoothly brought about the taget compound in almost quantitative yields under these mild and readily available conditions. We were delighted to find that the same beneficial results were again obtained in reaction employing quaternary substituted phenylthiolactams containing aliphatic and aromatic alkyl side chains by replacement of the solvent system. We further found that the use of β-substituted and α,β-disubstituted γ-phenylthiolactams as well as the aromatic one underwent convenient reactions to afford the corresponding desulfurized hydroxylactams in quite high yields. In light of the above outcome, we turned our attention to the development of novel and convenient synthetic method of isoindolobenzazepine alkaloid, chilenine and accomplished the total synthesis of natural chilenine. This process will be widely applicable to the synthesis of other fused alkaloidal natural products such as new antitumor antibiotics, UCS 1025 series containing a quaternary hydroxyl group α to the nitrogen.
该实验室最近的研究成果表明,SmI_2促进了芳香族内酰胺与羰基化合物的串联脱硫和高选择性偶联反应。因此,尽管在提高硫取代的内酰胺的多功能性方面已经取得了显著的进展,但令人惊讶的是,除了内缩醛类型的化合物之外,缺乏关于对简单刘易斯酸的反应性的研究。本文报道了在水介质中苯硫基取代的脂环族和芳香族内酰胺的刘易斯酸介导的串联反应,得到了γ-羟基化产物,并将其应用于异吲哚苯并氮杂天然产物chilenine的全合成,而FeCl_3和CuI的反应得到了所需的γ-羟基化产物,但产率较低。分别使用CuCl或CuBr对反应速率有显著的影响,并在这些温和和容易获得的条件下以几乎定量的产率顺利地得到目标化合物。我们高兴地发现,通过替换溶剂系统,使用含有脂肪族和芳香族烷基侧链的季取代苯基硫代内酰胺的反应再次获得了相同的有益结果。我们进一步发现,使用β-取代和α,β-二取代的γ-苯基硫代内酰胺以及芳香族的γ-苯基硫代内酰胺进行方便的反应,以相当高的产率得到相应的脱硫羟基内酰胺。基于上述研究结果,我们将研究重点转向了异吲哚苯并氮杂卓生物碱辣椒碱的合成方法,并完成了天然辣椒碱的全合成。该方法可广泛应用于其它稠合甾体类天然产物的合成,如新型抗肿瘤抗生素,含α位季羟基的UCS 1025系列。

项目成果

期刊论文数量(36)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Hidemi Yoda: "Novel and Stereoselective Asymmetric Synthesis of an Amino Sugar Analogue, Furanodictine A"Tetrahedron Letters. 45. 1599-1601 (2004)
Hidemi Yoda:“氨基糖类似物 Furanodictine A 的新颖和立体选择性不对称合成”四面体字母。
  • DOI:
  • 发表时间:
  • 期刊:
  • 影响因子:
    0
  • 作者:
  • 通讯作者:
Novel and Practical Asymmetric Synthesis of an Azetidine Alkaloid, Penaresidin B.
氮杂环丁烷生物碱 Penaresidin B 的新颖且实用的不对称合成。
  • DOI:
    10.1002/chin.200318188
  • 发表时间:
    2003
  • 期刊:
  • 影响因子:
    0
  • 作者:
    H. Yoda;T. Uemura;K. Takabe
  • 通讯作者:
    K. Takabe
Hidemi Yoda: "First Total Synthesis of a New Sesquiterpenoid Natural Product, (±)-3-(2,4-dihydroxybenzoyl)-4,5-dimethyl-5-(4,8-dimethyl-3(E),7(E)-nonadien-1-yl)tetrahydro-2-furanone"Tetrahedron Letters. 44. 1775-1777 (2003)
Hidemi Yoda:“首次全合成一种新的倍半萜类天然产物,(±)-3-(2,4-二羟基苯甲酰基)-4,5-二甲基-5-(4,8-二甲基-3(E),7( E)-壬二烯-1-基)四氢-2-呋喃酮”四面体快报。44. 1775-1777 (2003)
  • DOI:
  • 发表时间:
  • 期刊:
  • 影响因子:
    0
  • 作者:
  • 通讯作者:
Hidemi Yoda: "A New Entry for the Preparation of Substituted Aromatic Carbonyl Compounds Mediated by SmI_2"Synthetic Communications. 33. 1087-1094 (2003)
Hidemi Yoda:“SmI_2 介导的取代芳香族羰基化合物制备的新条目”合成通讯。
  • DOI:
  • 发表时间:
  • 期刊:
  • 影响因子:
    0
  • 作者:
  • 通讯作者:
Novel and Stereoselective Asymmetric Synthesis of an Amino Sugar Analogue, Furanodictine A
氨基糖类似物呋喃诺汀 A 的新颖立体选择性不对称合成
  • DOI:
  • 发表时间:
    2004
  • 期刊:
  • 影响因子:
    0
  • 作者:
    Hidemi Yoda;Hidemi Yoda
  • 通讯作者:
    Hidemi Yoda
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YODA Hidemi其他文献

YODA Hidemi的其他文献

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{{ truncateString('YODA Hidemi', 18)}}的其他基金

Development of novel bioactive organo-medicinal compounds against metabolic syndrome
开发抗代谢综合征的新型生物活性有机药物化合物
  • 批准号:
    22550032
  • 财政年份:
    2010
  • 资助金额:
    $ 2.43万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Asymmetric hydroxylation based on the Lewis acid-induced weak interaction and its application to the synthesis of natural products
基于路易斯酸弱相互作用的不对称羟基化及其在天然产物合成中的应用
  • 批准号:
    18550031
  • 财政年份:
    2006
  • 资助金额:
    $ 2.43万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
New Development of One-electron Transfer Reaction - Application to the Total Synthesis of Biologically Active Natural Products -
一电子转移反应新进展-在生物活性天然产物全合成中的应用-
  • 批准号:
    13640530
  • 财政年份:
    2001
  • 资助金额:
    $ 2.43万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Novel Methods for the construction of Biologically Active Natural Products based on a chiron-synthetic strategy
基于凯龙合成策略构建生物活性天然产物的新方法
  • 批准号:
    10640516
  • 财政年份:
    1998
  • 资助金额:
    $ 2.43万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Construction of Asymmetric Space and Catalytic Stereoselection with C_2-Symmetrical Molecules
C_2对称分子的不对称空间构建与催化立体选择
  • 批准号:
    06640765
  • 财政年份:
    1994
  • 资助金额:
    $ 2.43万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)

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通过真菌胺氧化酶和细菌醛氧化酶的偶联反应改善食品气味。
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SBIR Phase I: Development and commercialization of organic photocatalysts for light-driven C-N cross-coupling reaction
SBIR 第一阶段:用于光驱动 C-N 交叉偶联反应的有机光催化剂的开发和商业化
  • 批准号:
    1947053
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    2020
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Extension and challenging application of rapidly processing alkyl coupling reaction on secondary alkyl carbons
仲烷基碳上快速烷基偶联反应的扩展和挑战性应用
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镍催化醛与卤代烯交叉偶联反应的进展
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基于氧化酚偶联反应的哈苏巴南型生物碱的合成研究
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胺氧化酶与醛氧化酶偶联反应预防组胺中毒技术的建立
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固相交叉偶联反应简洁合成纳米石墨烯
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可见光光氧化还原催化自由基阳离子-自由基偶联反应
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