4-(benzyldimethylsilyl)but-3-yn-2-one | 850146-87-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-(benzyldimethylsilyl)but-3-yn-2-one
• 英文别名: 4-[Benzyl(dimethyl)silyl]but-3-yn-2-one
• CAS: 850146-87-1
• 化学式: C₁₃H₁₆OSi
• 分子量: 216.355
• InChiKey: DGTBJMMJZLHQPD-UHFFFAOYSA-N

物化性质

• 沸点：
  284.7±19.0 °C(Predicted)
• 密度：
  0.979±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.61
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-(benzyldimethylsilyl)but-3-yn-2-one 在 咪唑 、 4 A molecular sieve 、 chiral Ru catalyst 、 camphor-10-sulfonic acid 、 diethylzinc 、 (S,S)-(+)-2,6-双[2-(羟基二苯甲基)-1-吡咯烷基-甲基]-4-甲基苯酚 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 、 异丙醇 、 丙酮 为溶剂， 反应 60.17h， 生成 (3R,5R)-7-(Benzyl-dimethyl-silanyl)-5-(tert-butyl-dimethyl-silanyloxy)-3-hydroxy-hept-6-yn-2-one
  参考文献：
  名称：

  Dinuclear Asymmetric Zn Aldol Additions:  Formal Asymmetric Synthesis of Fostriecin

  摘要：

  Direct asymmetric aldol reactions constitute a powerful methodology for the efficient synthesis of complex natural products. Herein we report the first application of our recently reported dinuclear Zn-catalyzed direct aldol addition of alkynyl ketones to aldehydes in a short and efficient formal asymmetric synthesis of fostriecin, a potent cyctotoxic natural product. This work highlights not only the power of the aldol methodology but also the utility of the akynyl silane aldol adducts, as it is subsequently utilized in a vinyl silane cross-coupling reaction which affords the target molecule in 14 steps for the longest linear sequence in 8.5% overall yield.

  DOI：

  10.1021/ja042435i
• 作为产物：
  描述：

  苄基二甲基氯硅烷 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 5.0h， 生成 4-(benzyldimethylsilyl)but-3-yn-2-one
  参考文献：
  名称：

  Dinuclear Asymmetric Zn Aldol Additions:  Formal Asymmetric Synthesis of Fostriecin

  摘要：

  Direct asymmetric aldol reactions constitute a powerful methodology for the efficient synthesis of complex natural products. Herein we report the first application of our recently reported dinuclear Zn-catalyzed direct aldol addition of alkynyl ketones to aldehydes in a short and efficient formal asymmetric synthesis of fostriecin, a potent cyctotoxic natural product. This work highlights not only the power of the aldol methodology but also the utility of the akynyl silane aldol adducts, as it is subsequently utilized in a vinyl silane cross-coupling reaction which affords the target molecule in 14 steps for the longest linear sequence in 8.5% overall yield.

  DOI：

  10.1021/ja042435i

文献信息

• A Highly Convergent Total Synthesis of Leustroducsin B
  作者：Barry M. Trost、Berenger Biannic、Cheyenne S. Brindle、B. Michael O’Keefe、Thomas J. Hunter、Ming-Yu Ngai

  DOI：10.1021/jacs.5b07438

  日期：2015.9.16

  large variety of biological activities and unique structural features. An efficient and highly convergent total synthesis of Leustroducsin B was achieved in 17 longest linear and 39 total steps by disconnecting the molecule into three fragments having similar levels of complexity. These pieces were connected via a highly efficient chelate-controlled addition of a vinyl zincate to an α-hydroxy ketone and

  Leustroducsin B 具有多种生物活性和独特的结构特征。Leustroducsin B 的高效且高度收敛的全合成通过 17 个最长的线性步骤和 39 个总步骤实现，方法是将分子断开为具有相似复杂度水平的三个片段。这些片段通过高效螯合控制将乙烯基锌酸盐添加到 α-羟基酮和硅介导的交叉偶联来连接。中央和西部片段的立体化学通过锌-苯酚催化的羟醛反应和钯催化的不对称烯丙基烷基化以高产率和优异的催化进行设置。
• Re-orienting coupling of organocuprates with propargyl electrophiles from S_N2′ to S_N2 with stereocontrol
  作者：Barry M. Trost、Laurent Debien

  DOI：10.1039/c6sc01086e

  日期：——

  Diorganocuprate(i) reagents derived from lithiated heterocycles and CuCN react with enantioenriched secondary propagryl bromides to give the corresponding propargylated heterocycles.

  从锂化杂环和CuCN衍生的Diorganocuprate(i)试剂与手性丰富的二级丙炔基溴化物反应，得到相应的丙炔基化杂环化合物。
• Improved Method for the Synthesis of β-Carbonyl Silyl-1,3-Dithianes by the Double Conjugate Addition of 1,3-Dithiol to Propargylic Carbonyl Compounds
  作者：Sumit Mukherjee、Dimitra Kontokosta、Aditi Patil、Sivakumar Rallapalli、Daesung Lee

  DOI：10.1021/jo901950e

  日期：2009.12.4

  Base-mediated double Conjugate addition of 1,3-propane dithiol to various silylated propargylic aldehydes and ketones allows for an efficient and scalable synthesis of beta-carbonyl silyl-1,3-dithianes.
• Dinuclear Asymmetric Zn Aldol Additions:  Formal Asymmetric Synthesis of Fostriecin
  作者：Barry M. Trost、Mathias U. Frederiksen、Julien P. N. Papillon、Paul E. Harrington、Seunghoon Shin、Brock T. Shireman

  DOI：10.1021/ja042435i

  日期：2005.3.1

  Direct asymmetric aldol reactions constitute a powerful methodology for the efficient synthesis of complex natural products. Herein we report the first application of our recently reported dinuclear Zn-catalyzed direct aldol addition of alkynyl ketones to aldehydes in a short and efficient formal asymmetric synthesis of fostriecin, a potent cyctotoxic natural product. This work highlights not only the power of the aldol methodology but also the utility of the akynyl silane aldol adducts, as it is subsequently utilized in a vinyl silane cross-coupling reaction which affords the target molecule in 14 steps for the longest linear sequence in 8.5% overall yield.