3-(2-Propenoxy)-1-(trimethylsilyl)-1-propyne | 125002-58-6

• 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-(2-Propenoxy)-1-(trimethylsilyl)-1-propyne
• 英文别名: Trimethyl(3-prop-2-enoxyprop-1-ynyl)silane
• CAS: 125002-58-6
• 化学式: C₉H₁₆OSi
• 分子量: 168.311
• InChiKey: KNQHPMJHFITQEF-UHFFFAOYSA-N

物化性质

• 沸点：
  179.8±15.0 °C(Predicted)
• 密度：
  0.851±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.07
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-(2-Propenoxy)-1-(trimethylsilyl)-1-propyne 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以100%的产率得到(+/-)-1-(trimethylsilyl)hex-5-en-1-yn-3-ol
  参考文献：
  名称：

  Radical cyclization of (bromomethyl)dimethylsilyl propargyl ethers. Regio-, chemo- and stereoselectivity.

  摘要：

  Radical cyclization of (bromomethyl)dimethylsilyl propargyl ether derivatives 1 is a powerful reaction with a high degree of regio-, chemo-, and stereoselectivity. Trisubstituted olefins 3, cyclopentene derivatives 5, and diquinane system 7j are obtained in good yields by a judicious choice of unsaturated substituents. Triquinane frameworks could be obtained stereoselectively from a suitable acyclic substrate of type 1 in a one-pot reaction. First attempts have not yet allowed us to aim at this goal due to interesting (1,5) hydrogen transfers. Moreover, we have intercepted, for the first time, the alpha-cyclopropyl radical which is involved in the Stork-Beckwith mechanism of the 5-versus 6-membered ring formation in the vinyl radical cyclization.

  DOI：

  10.1021/jo00037a026
• 作为产物：
  描述：

  三甲硅基丙炔醇 、 3-溴丙烯 在 六甲基磷酰三胺 、 乙基溴化镁 作用下， 以 四氢呋喃 为溶剂， 以6 g的产率得到3-(2-Propenoxy)-1-(trimethylsilyl)-1-propyne
  参考文献：
  名称：

  [EN] TR-BETA MODULATORS, PHARMACEUTICAL COMPOSITIONS, AND THERAPEUTIC APPLICATIONS
  [FR] MODULATEURS DU TR-BÊTA, COMPOSITIONS PHARMACEUTIQUES ET APPLICATIONS THÉRAPEUTIQUES

  摘要：

  Provided herein are TRβ modulators, for example, a compound of Formula (I), and pharmaceutical compositions thereof. Also provided herein are methods of their use for treating, preventing, or ameliorating one or more symptoms of a TRβ-mediated disorder, disease, or condition.

  公开号：

  WO2023023474A1

文献信息

• Titanocene- and zirconocene-mediated cyclization of allyl propargyl ethers. Stereoselective synthesis of 3-methylenetetrahydrofurans
  作者：Katsukiyo Miura、Masashi Funatsu、Hiroshi Saito、Hajime Ito、Akira Hosomi

  DOI：10.1016/s0040-4039(96)02128-4

  日期：1996.12

  Low-valent titanium and zirconium reagents in situ prepared from metallocene dichlorides (Cp2MCl2: M = Ti, Zr) and magnesium powder activated by 1,2-dibromoethane smoothly reacted with allyl propargyl ethers to afford 3-methylenetetrahydrofurans in good yields. It is noteworthy that the Cp2Zr- and Cp2Ti-mediated cyclizations proceed with inverse stereoselectivity.

  由茂金属二氯化物（Cp 2 MCl 2：M = Ti，Zr）和被1,2-二溴乙烷活化的镁粉原位制备的低价钛和锆试剂与烯丙基炔丙基醚平稳反应，以高收率得到3-亚甲基四氢呋喃。值得注意的是，Cp 2 Zr和Cp 2 Ti介导的环化反应的立体选择性反演。
• SmI2-Mediated cyclization of vinyl radicals
  作者：Laura Capella、Pier Carlo Montevecchi

  DOI：10.1016/s0040-4039(00)74429-7

  日期：1994.11

  SmI2-Mediated formation of vinyl radicals give stereoselective 5- or 6-exo cyclization on the intramolecular carbon-carbon triple bond in addition to 1,5-hydrogen shift; further reduction of the resulting alkyl radical would lead to a transient carbanion which can undergo [2,3] sigmatropic Wittig rearrangement.

  SmI 2-介导的乙烯基自由基的形成，除了1,5-氢转移外，还对分子内碳-碳三键进行了立体选择性的5或6-exo环化反应；进一步还原生成的烷基会导致短暂的碳负离子，该碳会经历[2,3]σ维蒂希重排。
• Ru₃(CO)₁₂-Catalyzed Cyclocarbonylation of 1,6-Enynes to Bicyclo[3.3.0]octenones
  作者：Tsumoru Morimoto、Naoto Chatani、Yoshiya Fukumoto、Shinji Murai

  DOI：10.1021/jo970231x

  日期：1997.5.1
• Cyclizations and Rearrangements of Samarium Diiodide-Generated Vinyl Radicals
  作者：Laura Capella、Pier Carlo Montevecchi、Maria Luisa Navacchia

  DOI：10.1021/jo00128a013

  日期：1995.11

  Vinyl bromides 1, 5, 15, 20, 23, 27, 33a,b, 41a-c, 44a-c, 46a,b, 52a,b, 55a, 56a,b, and 60a,b react with samarium diiodide in THF and/or acetonitrile to give the corresponding vinyl radicals. Radicals 3, 7, and 16 afforded products deriving from cyclization on the adjacent triple bond in a 5-(pi-exo)exo, 6-(pi-endo)exo, and 6-(pi-exo)exo mode, respectively. Radical 7 undergoes competitive 1,5-hydrogen translocation. Vinyl radicals 21 and 24 readily cyclize on the proximal double bond, leading to 5- and 6-membered rings, respectively. Thienyl-substituted radical 28 leads to a product deriving from 5-exo cyclization on the thiophene ring and subsequent beta-fission of the C-S bond, whereas thienyl-substituted radicals 34a,b undergo almost exclusively 1,5-hydrogen translocation. Aryl-substituted radicals obtained from vinyl bromides 41, 44, 46, 52, and 55 do not form any products deriving from 5-exo or 6-exo cyclization (or ipso cyclization). Finally, naphthyl-substituted radicals 57a and 61a give only direct reduction products, whereas the radical 61b affords, in addition to the direct reduction product, a rearranged product deriving from a 1,3-radical migration of the naphthylthio group. Evidence is reported for the reduction of EWG-substituted benzene rings and thio-substituted naphthalene rings to radical anions, which can fragment on the side chain with the elimination of allyl radicals. alpha-Oxy(and alpha-thio)-substituted radicals deriving from 1,5-shift rearrange to alcohols (and thiols) through a Wittig rearrangement or a cyclization/fragmentation process.
• Pearson Anthony J., Dubbert Robert A., Organometallics, 13 (1994) N 5, S 1656-1661
  作者：Pearson Anthony J., Dubbert Robert A.

  DOI：——

  日期：——