3-(trimethylsilyl)-2-propenylacetate | 86422-21-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-(trimethylsilyl)-2-propenylacetate
• 英文别名: [(E)-3-trimethylsilylprop-2-enyl] acetate
• CAS: 86422-21-1
• 化学式: C₈H₁₆O₂Si
• 分子量: 172.299
• InChiKey: KWDYUHNACUTFNF-FNORWQNLSA-N

物化性质

• 沸点：
  188.0±23.0 °C(Predicted)
• 密度：
  0.890±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.98
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  3-(trimethylsilyl)-2-propenylacetate 以71%的产率得到
  参考文献：
  名称：

  Miyazaki Yasushi, Hotta Hiroyasu, Sato Fumie, Tetrahedron Lett, 35 (1994) N 25, S 4389- 4392

  摘要：

  DOI：
• 作为产物：
  描述：

  Carbonic acid ethyl ester (E)-3-trimethylsilanyl-allyl ester 以50%的产率得到
  参考文献：
  名称：

  Miyazaki Yasushi, Hotta Hiroyasu, Sato Fumie, Tetrahedron Lett, 35 (1994) N 25, S 4389- 4392

  摘要：

  DOI：

文献信息

• Asymmetric Claisen Rearrangements Enabled by Catalytic Asymmetric Di(allyl) Ether Synthesis
  作者：Scott G. Nelson、Kan Wang

  DOI：10.1021/ja058172p

  日期：2006.4.5

  Merging the catalytic asymmetric synthesis of di(allyl) ethers with ensuing olefin isomerization-Claisen rearrangement (ICR) reactions provides a convenient, two-step route to asymmetric aliphatic Claisen rearrangements from easily obtained starting materials. These reactions deliver the 2,3-disubstituted 4-pentenal derivatives characteristic of aliphatic Claisen rearrangements with excellent relative

  将二（烯丙基）醚的催化不对称合成与随后的烯烃异构化-克莱森重排 (ICR) 反应相结合，为从容易获得的起始材料进行不对称脂肪族克莱森重排提供了一种方便的两步路线。这些反应提供了脂肪族克莱森重排的 2,3-二取代 4-戊烯醛衍生物特征，具有出色的相对和绝对立体控制。(+)-calopin 二甲醚的催化对映选择性合成证明了该反应技术在不对称合成企业中的实用性。
• A new synthesis of medium-membered lactones via intramolecular condensation of α(-chlorosulfides containing an ester group and allylsilanyl moiety
  作者：Makoto Wada、Takahide Shigehisa、Kin-ya Akiba

  DOI：10.1016/s0040-4039(00)98900-7

  日期：1985.1

  Medium-membered lactones (8∼11 membered rings) were obtained in good yields by EtAlCl2-promoted intramolecular condensation of α-chlorosulfides containing an ester group and allylsilanyl moiety without the need for high dilution conditions.

  通过EtAlCl 2促进的含有酯基和烯丙基甲硅烷基部分的α-氯硫化物的分子内缩合，无需高稀释条件，就可以以高收率获得中成员内酯（8-11元环）。
• Chiral Phosphoric Acid-Catalyzed Enantio- and Diastereoselective Allylboration of Aldehydes with β,γ-Substituted Allylboronates
  作者：Jinping Yuan、Pankaj Jain、Jon C. Antilla

  DOI：10.1021/acs.joc.2c00764

  日期：2022.6.17

  The catalytic asymmetric addition of β,γ-substituted allylboronates to aldehydes has been described. Promoted by 5 mol % chiral phosphoric acid, the reactions were broadly applicable, scalable, and efficient, allowing for the formation of 3,4-anti/syn-homoallylic alcohols bearing adjacent tertiary or quaternary stereogenic centers in a highly enantio- and diastereoselective manner (≤99% ee and dr >20:1)

  已经描述了 β,γ-取代的烯丙基硼酸酯对醛的催化不对称加成。在 5 mol% 手性磷酸的促进下，该反应具有广泛的适用性、可扩展性和高效性，允许以高度对映和非对映选择性的方式形成带有相邻叔或季立体中心的 3,4-反/同-高烯丙醇（≤99% ee 和 dr >20:1）。涉及手性磷酸的刚性椅子状过渡态有助于高度控制的反应。
• Novel cyclization by stannyl anion generated from (trimethylsilyl)tributylstannane (Me3SiSnBu3) and fluoride ion. Application to natural product synthesis
  作者：Miwako Mori、Naohiro Isono、Naotake Kaneta、Masakatsu Shibasaki

  DOI：10.1021/jo00063a012

  日期：1993.5

  Stannyl anion, generated from Me3SiSnBu3 and (Et2N)3S+TMSF2- (TASF) or CsF in DMF, was quite effective for generation of an aryl or vinyl anion, which reacted with a carbonyl group intramolecularly to provide the useful cyclized product in good yield.
• Palladium(0)-catalyzed alkoxycarbonylation of allyl phosphates and acetates
  作者：Shunichi Murahashi、Yasushi Imada、Yuki Taniguchi、Shinya Higashiura

  DOI：10.1021/jo00058a040

  日期：1993.3

  Palladium-catalyzed alkoxycarbonylation of allyl phosphates under CO (1 atm) at 50-degrees-C proceeds highly efficiently to give the corresponding beta,gamma-unsaturated esters. The carbonylation of geranyl phosphate ((E)-11) under CO (1 atm) at 50-degrees-C gave ethyl ester of homogeranic acid ((E)-12) stereoselectively. The carbonylation takes place at the least substituted allylic positions with inversion of configuration. Typically, the methoxycarbonylation of cis-5-(methoxycarbonyl)-2-cyclohexen-1-yl phosphate (cis-16) gave trans-dimethyl 2-cyclohexene-1,5-dicarboxylate (trans-17) selectively. Alkoxycarbonylation of allyl acetates is performed for the first time in the presence of a catalytic amount of bromide ion. The reaction can be rationalized by assuming the mechanism which involves oxidative addition of palladium(0) species to allyl acetates to give pi-allylpalladium acetate, fast ligand exchange of the acetate with bromide, insertion of carbon monoxide to give acylpalladium species, and alkoxylation.