Diastereoselective Construction of Contiguous Chilal Centers by the Aldol Reaction of Acylsilane Silyl Enol Ethers.

通过酰基硅烷甲硅烷基烯醇醚的羟醛反应非对映选择性构建连续手性中心。

基本信息

  • 批准号:
    03650694
  • 负责人:
  • 金额:
    $ 1.22万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)
  • 财政年份:
    1991
  • 资助国家:
    日本
  • 起止时间:
    1991 至 1992
  • 项目状态:
    已结题

项目摘要

There has been considerable interest in recent years in the stereoselective formation of multiple chiral centers using aldol reaction between prochiral enolates and aldehydes. We disclosed here an convenient method of diastereoselective construction of the three or four contiguous chiral centers using the Lewis acid mediated reaction of acylsilane silyl enol ethers (I) with acetals and the subsequent nucleophilic addition to the carbonyl group of the resulting acylsilanes (II).Treatment of E-or Z-acylsilane silyl enol ethers (I) derived from acylsilanes having enolizable methylene proton with a mixture of aldehyde dimethylacetals and TiCl_4 in dichloromethane gave the corresponding 2,3-anti-3-methoxy-1-silyl-1-alkanones (II) in high diastereo excess,independent of the double bond stereochemistry of I used. The similar reaction of E-I with d,1-phenylpropionealdehyde afforded 2,3-syn-3,4-syn-3-methoxy-1-silyl-1-butanal (V) in high stereoselectivity.The resulting acylsilane 2,3-anti-II and 2,3-syn-3,4-syn-V were subjected to the nucleophilic reaction with alkyl or phenyllithium to yield the corresponding 3-methoxy-1-silyl-1-alkanols with three and four contiguous asymmetric centers (III and VI, respectively) stereoselectively. The protiodesilylation of III and VI with F^- reagent to afford the corresponding 1,2-anti-al- kanols with three and four contiguous asymmetric centers, IV and VII in 95-99% diastereo excess.
近年来,利用前手性烯醇和醛之间的醛醇反应立体选择性形成多个手性中心的研究引起了人们的极大兴趣。我们在这里公开了一种方便的非对映选择性构建三个或四个连续手性中心的方法,使用刘易斯酸介导的酰基硅烷硅烯醇醚(I)与缩醛的反应,以及随后在生成的酰基硅烷(II)的羰基上亲核加成。由具有可烯化亚甲基质子的酰基硅烷衍生的e -或z -酰基硅烷硅烯醇醚(I)与乙醛二甲基缩醛和TiCl_4的混合物在二氯甲烷中处理,得到相应的2,3-反-3-甲氧基-1-硅基-1-烷酮(II),具有高度的非立体过量,与I所使用的双键立体化学无关。E-I与d,1-苯丙烯醛的类似反应产生2,3- syn3,4 - syn3 -甲氧基-1-硅基-1-丁醛(V)具有高立体选择性。得到的2,3-抗- ii和2,3-syn-3,4-syn- v型酰基硅烷与烷基或苯基锂发生亲核反应,立体选择性地生成具有3个和4个连续不对称中心(分别为III和VI)的3-甲氧基-1-硅基-1-烷醇。用F^-试剂对III和VI进行原硅酰化反应,得到相应的具有3个和4个连续不对称中心的1,2-抗al- kanols, IV和VII在95-99%的非映体过量。

项目成果

期刊论文数量(11)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Tadashi Nakajima: "Diastereoselective Construction of Three Contiguous Chiral Centers using Acylsilane Silyl Enol Ethers" Bull.Chem.Soc.Jpn.,.
Tadashi Nakajima:“使用酰基硅烷甲硅烷基烯醇醚非对映选择性构建三个连续手性中心”Bull.Chem.Soc.Jpn.,。
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    0
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  • 通讯作者:
Tadashi Nakajima: "Diastereoselective Construction of Four Contiguous Chiral Centers by the Reaction of Acylsilane Silyl Enol Ethers with a-Chiral Aldehydeacetal." Chem. Lett.
Tadashi Nakajima:“通过酰基硅烷甲硅烷基烯醇醚与 a-手性醛缩醛的反应非对映选择性构建四个连续手性中心。”
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    0
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Tadashi Nakajima: "Diastereoselective Construction of Four Contiguous Chiral Centers by the Reaction of Acylsilane Silyl Enol Ethers with α-Chiral Aldehydeacetal." Chem.Lett.
Tadashi Nakajima:“通过酰基硅烷甲硅烷基烯醇醚与 α-手性醛缩醛的反应非对映选择性构建四个连续手性中心。”
  • DOI:
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    0
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  • 通讯作者:
Tadashi Nakajima: "Diastereoselective Construction of Three Contiguous Chiral Centers using Acylsilane Silyl Enol Ethers." Bull. Chem. Soc. Jpn.
Tadashi Nakajima:“使用酰基硅烷甲硅烷基烯醇醚非对映选择性构建三个连续的手性中心。”
  • DOI:
  • 发表时间:
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  • 影响因子:
    0
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  • 通讯作者:
Tadashi Nakajima: "Reaction of Acylsilanes with Meta-stable Phosphonium ylides and Phosphonium diylides." Bull.Chem.Soc.Jpn.
Tadashi Nakajima:“酰基硅烷与亚稳态磷叶立德和二叶立德的反应。”
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    0
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NAKAJIMA Tadashi其他文献

NAKAJIMA Tadashi的其他文献

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{{ truncateString('NAKAJIMA Tadashi', 18)}}的其他基金

Genetic background of ventricular tachyarrhythmias associated with acute myocardial ischemia
急性心肌缺血相关室性快速心律失常的遗传背景
  • 批准号:
    23591030
  • 财政年份:
    2011
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Paleomagnetism of Widespread Marker Tephras and High Resolution Magnetostratigraphy
广泛分布的标记火山灰的古地磁学和高分辨率磁性地层学
  • 批准号:
    16500637
  • 财政年份:
    2004
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Systematics Searches for Brown Dwarfs and Planets
褐矮星和行星的系统学搜索
  • 批准号:
    14540232
  • 财政年份:
    2002
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Magnetic Chart Deduced from Paleomagnetism of Widespread Marker Tephras
从广泛分布的标记火山石的古地磁学推导出的磁图
  • 批准号:
    12680158
  • 财政年份:
    2000
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Planning a Large-Scale Near-Infrared Survey
规划大规模近红外测量
  • 批准号:
    10640239
  • 财政年份:
    1998
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Isomagnetic Chart Deduced from Remanent Magnetization of Widespread Marker Tephras and Geomagnetic Secular Variation in the Japanese Islands
从广泛分布的标记火山灰的剩磁和日本列岛地磁长期变化推导出的等磁图
  • 批准号:
    05835005
  • 财政年份:
    1993
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)
Novel preparation method and synthetic applications of cyclopropyl trimethylsilyl ketones
环丙基三甲基硅酮的制备新方法及合成应用
  • 批准号:
    62550627
  • 财政年份:
    1987
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)

相似海外基金

Development of New Type of Polymerizations and Polymer Reactions on the Basis of Acylsilane Chemistry
基于酰基硅烷化学的新型聚合和聚合物反应的发展
  • 批准号:
    20K05601
  • 财政年份:
    2020
  • 资助金额:
    $ 1.22万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
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