2-trimethylsilylethyl 2,3-butadienoate | 850695-12-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-trimethylsilylethyl 2,3-butadienoate
• CAS: 850695-12-4
• 化学式: C₉H₁₆O₂Si
• 分子量: 184.31
• InChiKey: LHTVRLPMBNUBGQ-UHFFFAOYSA-N

物化性质

• 沸点：
  224.8±10.0 °C(Predicted)
• 密度：
  0.877±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.21
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  苯甲醛 、 2-trimethylsilylethyl 2,3-butadienoate 在 三环戊基膦 作用下， 以 氯仿 为溶剂， 反应 48.0h， 以58%的产率得到6-苯基吡喃-2-酮
  参考文献：
  名称：

  Phosphine-Catalyzed Synthesis of 6-Substituted 2-Pyrones:  Manifestation of E/Z-Isomerism in the Zwitterionic Intermediate

  摘要：

  We report a one-step phosphine-catalyzed annulation between aldehydes and ethyl allenoate to form 6-substituted 2-pyrones. The mechanistic rationale for this reaction requires explicit discussion of the EIZ-isomerism of the zwitterionic intermediate formed by the addition of a phosphine to the allenoate. Sterically demanding trialkylphosphines facilitate the shift of equilibrium toward the E-isomeric zwitterion and lead to the formation of 6-substituted 2-pyrones. Various aromatic as well as aliphatic aldehydes undergo the transformation in moderate to excellent yield.

  DOI：

  10.1021/ol050946j
• 作为产物：
  描述：

  2-(三甲硅基)乙醇 在 sodium carbonate 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 168.0h， 生成 2-trimethylsilylethyl 2,3-butadienoate
  参考文献：
  名称：

  Phosphine-Catalyzed Synthesis of 1,3-Dioxan-4-ylidenes

  摘要：

  A phosphine-catalyzed reaction of an allenoate with aldehydes furnished (2,6-diaryl-[1,3]dioxan-4-ylidene)-acetates 4 in excellent to moderate yields with complete diastereoselectivity and high E/Z-selectivities. Upon removal of the acetal functionality in this domino reaction product 4, delta-hydroxy-beta-ketoester 11 was obtained. The reported vinylphosphonium-based approach provides a new way to achieve a synthesis of 6-hydroxy-beta-ketoesters that differs from the classical dianion-based approach.

  DOI：

  10.1021/ol050203y

文献信息

• Bridged [2.2.1] bicyclic phosphine oxide facilitates catalytic γ-umpolung addition–Wittig olefination
  作者：Kui Zhang、Lingchao Cai、Zhongyue Yang、K. N. Houk、Ohyun Kwon

  DOI：10.1039/c7sc04381c

  日期：——

  A novel bridged [2.2.1] bicyclic phosphine oxide, devised to circumvent the waste generation and burdens of purification that are typical of reactions driven by the generation of phosphine oxides, has been prepared in three steps from commercially available cyclopent-3-ene-1-carboxylic acid. The performance of this novel phosphine oxide was superior to those of current best-in-class counterparts, as

  一种新型桥接 [2.2.1] 双环氧化膦，旨在规避由氧化膦产生驱动的典型反应的废物产生和纯化负担，由市售 cyclopent-3-ene- 分三步制备。 1-羧酸。这种新型氧化膦的性能优于当前同类最佳同类产品，这一点通过对其硅烷介导还原的动力学分析进行了实验验证。它已成功应用于无卤化物/无碱催化 γ-umpolung 加成 - 联烯酸酯和 2-酰胺基苯甲醛的 Wittig 烯化反应，高效生产 1,2-二氢喹啉。一种 1,2-二氢喹啉产品被转化为已知的抗结核呋喃喹啉。
• Phosphine-Mediated Iterative Arene Homologation Using Allenes
  作者：Kui Zhang、Lingchao Cai、Xing Jiang、Miguel A. Garcia-Garibay、Ohyun Kwon

  DOI：10.1021/jacs.5b07403

  日期：2015.9.9

  A PPh3-mediated multicomponent reaction between o-phthalaldehydes, nucleophiles, and monosubstituted allenes furnishes functionalized non-C-2-symmetric naphthalenes in synthetically useful yields. When the o-phthalaldehydes were reacted with 1,3-disubstituted allenes in the presence of PPh2Et, naphthalene derivatives were also obtained in up to quantitative yields. The mechanism of the latter transformation is straightforward: aldol addition followed by Wittig olefination and dehydration. The mechanism of the former is a tandem gamma-umpolung/aldol/Wittig/dehydration process, as established by preparation of putative reaction intermediates and mass spectrometric analysis. This transformation can be applied iteratively to prepare anthracenes and tetracenes using carboxylic acids as pronucleophiles.