3-(methyldiphenylsilyl)propiolaldehyde | 1198205-71-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 3-(methyldiphenylsilyl)propiolaldehyde
• 英文别名: 3-[Methyl(diphenyl)silyl]prop-2-ynal
• CAS: 1198205-71-8
• 化学式: C₁₆H₁₄OSi
• 分子量: 250.372
• InChiKey: UICRPSDMZTWDHU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.62
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 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：

  1,3-丙二硫醇 、 3-(methyldiphenylsilyl)propiolaldehyde 在 aluminum oxide 作用下， 以 四氢呋喃 为溶剂， 以93%的产率得到2-(2-(methyldiphenylsilyl)-1,3-dithian-2-yl)acetaldehyde
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo901950e
• 作为产物：
  描述：

  3-(methyldiphenylsilyl)-2-propyn-1-ol 在 2-碘酰基苯甲酸 作用下， 以 二甲基亚砜 为溶剂， 以65%的产率得到3-(methyldiphenylsilyl)propiolaldehyde
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo901950e

文献信息

• Diarylprolinol in an Asymmetric, Direct Cross-Aldol Reaction with Alkynyl Aldehydes
  作者：Yujiro Hayashi、Masahiro Kojima、Yusuke Yasui、Yuta Kanda、Takasuke Mukaiyama、Hiroki Shomura、Daichi Nakamura、Ritmaleni、Itaru Sato

  DOI：10.1002/cctc.201300390

  日期：2013.10

  The direct cross‐aldol reaction of alkynyl aldehydes catalyzed by a trifluoromethylated diarylprolinol provides a practical route for the highly enantioselective synthesis of chiral β‐alkynyl‐β‐hydroxy aldehydes. Good anti selectivity and excellent enantioselectivity were obtained in the reactions of silylpropynals, which afford synthetically useful chiral building blocks.

  三氟甲基化的二芳基脯氨醇催化的炔醛的直接交叉羟醛缩合反应为手性β-炔基-β-羟基醛的高对映选择性合成提供了一条可行的途径。在甲硅烷基丙炔的反应中获得了良好的抗选择性和优异的对映选择性，这提供了合成上有用的手性结构单元。
• Highly Enantioselective Access to <i>syn</i>-α,γ-Dihydroxycarbonyl Building Blocks via Organocatalyst-mediated Aldol Reaction as a Key Step
  作者：Yujiro Hayashi、Xiaoling Wang、Genki Kawauchi

  DOI：10.1246/cl.200304

  日期：2020.8.5

  An efficient synthesis of chiral syn-α,γ-dihydroxycarbonyl units from readily available achiral precursors in three pots under mild conditions was developed. This method explored the asymmetric direct cross-aldol reaction of two different aldehydes in the presence of an organocatalyst to generate a chiral β-hydroxyaldehyde, which was converted into a 4-nitromethyl-1,3-dioxane derivative as a diastereo-mixture via a sequence of nitroalkane addition and acetalization. The 4-nitromethyl-1,3-dioxane derivative was then transformed either to a carboxylic ester or to an aldehyde/ketone. The chiral syn-α,γ-dialkoxy esters and aldehydes/ketones were all obtained with excellent enantiopurity and diastereoselectivity after a base-promoted epimerization.

  本研究开发了一种在温和条件下，通过三个罐子从容易获得的非手性前体中高效合成手性合成-α,γ-二羟基羰基单元的方法。该方法探索了在有机催化剂存在下两种不同醛的不对称直接交醛反应，生成手性 β-羟基醛，通过一连串的硝基烷烃加成和缩醛反应将其转化为 4-硝基甲基-1,3-二氧六环衍生物的非对映混合物。然后，4-硝基甲基-1,3-二恶烷衍生物被转化为羧酸酯或醛/酮。经过碱促进的外延化反应后，得到的手性合成-α,γ-二烷氧基酯和醛/酮都具有极好的对映体纯度和非对映选择性。
• Two-Pot Synthesis of Chiral 1,3-<i>syn</i> -Diols through Asymmetric Organocatalytic Aldol and Wittig Reactions Followed by Domino Hemiacetal/Oxy-Michael Reactions
  作者：Yujiro Hayashi、Takanobu Saitoh、Hiromu Arase、Genki Kawauchi、Naohiro Takeda、Yasuharu Shimasaki、Itaru Sato

  DOI：10.1002/chem.201705930

  日期：2018.4.3

  two‐pot synthetic method to construct the chiral syn‐1,3‐diol unit has been developed from three aldehydes and either Wittig or Horner–Wadsworth–Emmons reagents. In the first pot, chiral δ‐hydroxy α,β‐unsaturated ketones are synthesized with excellent enantioselectivity by the organocatalyst‐mediated asymmetric direct aldol reaction of two different aldehydes, followed by either Wittig or Horner–Wadsworth–Emmons

  由三种醛和Wittig或Horner-Wadsworth-Emmons试剂开发了一种两锅法合成手性syn -1,3-二醇单元的方法。在第一个罐中，通过有机催化剂介导的两种不同醛的不对称直接羟醛直接反应，接着以Wittig或Horner-Wadsworth-Emmons反应合成具有出色对映选择性的手性δ-羟基α，β-不饱和酮。在第二个锅中，在NaClO 4和催化量的Bi（OTf）3（OTf =三氟甲磺酸盐）存在下，用醛进行多米诺乙缩醛反应，然后进行氧-迈克尔反应，以提供手性1,3-辛具有出色的非对映选择性的-二醇衍生物。通过使用本发明的方法作为关键步骤，有效地合成了薯C皂苷C和矢车菊二醇A。
• 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.