1-<2-bromo-2-propen-1-yloxy>-3-trimethylsilyl-prop-2-yne | 145852-63-7

• 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: 1-<2-bromo-2-propen-1-yloxy>-3-trimethylsilyl-prop-2-yne
• 英文别名: (3-(2-bromoallyloxy)prop-1-ynyl)trimethylsilane；3-(2-Bromoprop-2-enoxy)prop-1-ynyl-trimethylsilane
• CAS: 145852-63-7
• 化学式: C₉H₁₅BrOSi
• 分子量: 247.207
• InChiKey: INMBJNUHYQHUPL-UHFFFAOYSA-N

物化性质

• 沸点：
  233.7±20.0 °C(Predicted)
• 密度：
  1.173±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.79
• 重原子数：
  12
• 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：

  1-<2-bromo-2-propen-1-yloxy>-3-trimethylsilyl-prop-2-yne 在 正丁基锂 、 氯化铵 作用下， 生成 5-Bromo-1-(trimethylsilyl)hex-5-en-1-yn-3-ol
  参考文献：
  名称：

  阿维菌素六氢苯并呋喃部分的合成I.模型研究

  摘要：

  串联自由基环化已被用于构建阿维菌素中六氢苯并呋喃部分合成的模型。

  DOI：

  10.1016/s0040-4020(01)88314-9
• 作为产物：
  描述：

  三甲基氯硅烷 、 1-<2-bromo-2-propen-1-yloxy>-prop-2-yne 在 正丁基锂 作用下， 生成 1-<2-bromo-2-propen-1-yloxy>-3-trimethylsilyl-prop-2-yne
  参考文献：
  名称：

  阿维菌素六氢苯并呋喃部分的合成I.模型研究

  摘要：

  串联自由基环化已被用于构建阿维菌素中六氢苯并呋喃部分合成的模型。

  DOI：

  10.1016/s0040-4020(01)88314-9

文献信息

• A Cascade Palladium-Mediated Cross-Coupling/Electrocyclization Approach to the Construction of Fused Bi- and Tricyclic Rings
  作者：S. B. Jennifer Kan、Edward A. Anderson

  DOI：10.1021/ol8007952

  日期：2008.6.5

  A versatile palladium-catalyzed cyclization/cross-coupling/electrocyclization strategy for the synthesis of fused bi- and tricyclic ring systems is described. Excellent yields of the polycyclic products are obtained with a range of tethering ring sizes and functionality, including an unprecedented 5,6,4,5-fused tetracycle. The reaction mechanism features two unusual palladium-mediated isomerizations

  描述了一种通用的钯催化的环化/交叉偶联/电环化策略，用于合成稠合的双环和三环系统。通过一系列的束缚环大小和功能性（包括前所未有的5,6,4,5-稠合四环），可获得优异的多环产物收率。在电环化之前，反应机理具有两个不同寻常的钯介导的异构化作用。
• 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。
• 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.
• A synthesis of the hexahydrobenzofuran portion of the avermectins I. Model studies
  作者：Philip J. Parsons、Paul Willis、S.C. Eyley

  DOI：10.1016/s0040-4020(01)88314-9

  日期：1992.1

  A tandem radical cyclisation has been used to construct a model for the synthesis of the hexahydrobenzofuran moiety present in the avermectins.

  串联自由基环化已被用于构建阿维菌素中六氢苯并呋喃部分合成的模型。