(E)-8-(tert-butyldimethylsilanyloxy)-6-methyl-1-trimethylsilanyloct-5-en-1-yne | 78592-78-6

• 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: (E)-8-(tert-butyldimethylsilanyloxy)-6-methyl-1-trimethylsilanyloct-5-en-1-yne
• 英文别名: tert-butyl-dimethyl-[(E)-3-methyl-8-trimethylsilyloct-3-en-7-ynoxy]silane
• CAS: 78592-78-6
• 化学式: C₁₈H₃₆OSi₂
• 分子量: 324.654
• InChiKey: QSMBQUROBPHFQI-GHRIWEEISA-N

物化性质

• 沸点：
  340.9±30.0 °C(Predicted)
• 密度：
  0.853±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.01
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  (E)-8-(tert-butyldimethylsilanyloxy)-6-methyl-1-trimethylsilanyloct-5-en-1-yne 在 咪唑 、 碘 、 溶剂黄146 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 生成 (E)-8-iodo-6-methyl-1-trimethylsilyl-5-octen-1-yne
  参考文献：
  名称：

  Efficient Assembly of the Phomactin Core via Two Different Macrocyclization Protocols

  摘要：

  [GRAPHICS]The core structure of phomactins C and D was assembled by an efficient strategy starting from 3,4-dimethylcyclohexen-2-one. Key reactions include (1) a high yielding and highly diastereoselective Michael addition of a mixed cuprate, (2) a carbonylative alkyne-enoltriflate coupling or an intramolecular addition of an acetylide onto an aldehyde to form the macrocycle, (3) chemoselective Michael addition of a cuprate to an enynone, to give the carbon framework of desformyl phomactin C or D, and finally (4) regioselective addition of a thia-nucleophile to the more reactive beta -position of the resulting dienone.

  DOI：

  10.1021/ol0163833
• 作为产物：
  描述：

  4-(叔丁基二甲基硅杂氧基)-1-丁炔 在 四(三苯基膦)钯 、 二氯二茂锆 碘 作用下， 生成 (E)-8-(tert-butyldimethylsilanyloxy)-6-methyl-1-trimethylsilanyloct-5-en-1-yne
  参考文献：
  名称：

  A versatile and selective route to difunctional trisubstituted (E)-alkene synthons via zirconium-catalyzed carboalumination of alkynes

  摘要：

  DOI：

  10.1021/jo00333a041

文献信息

• Synthetic studies towards the phomactins. Concise syntheses of the tricyclic furanochroman and the oxygenated bicyclo[9.3.1]pentadecane ring systems in phomactin A
  作者：Kevin M Foote、Christopher J Hayes、Matthew P John、Gerald Pattenden

  DOI：10.1039/b307985f

  日期：——

  A concise synthesis of the tricyclic furanochroman unit 3 found in the PAF antagonist phomactin A (1) isolated from the marine fungus Phoma sp., is described. In complementary studies, a variety of synthetic routes towards the bicyclo[9.3.1]pentadecane ring system 4 in phomactin A were explored. These studies culminated in a synthesis of the substituted ring system 79 containing all the carbon atoms

  描述了从海洋真菌Phoma sp。分离出的PAF拮抗剂phomactin A（1）中发现的三环呋喃喃喃单元3的简明合成。在补充研究中，探索了多种在光蛋白A中合成双环[9.3.1]十五烷环系统4的合成途径。这些研究最终合成了取代环系统79，该取代环系统包含所有的碳原子和所有必要的氧中心，以形成光蛋白A本身。
• Synthesis of the Oxygenated Bicyclo[9.3.1]pentadecane Ring System of Phomactin A using Chromium (II)-mediated Macrocyclisation and Ring Closure Metathesis
  作者：Kevin M. Foote、Matthew John、Gerald Pattenden

  DOI：10.1055/s-2001-11403

  日期：——

  Treatment of the aldehyde vinyl iodides 17, 19 a and 19 b in DMSO with CrCl2-NiCl2 resulted in their macrocyclisation to the oxygenated ring systems 18, 20, and 21 respectively (43-63%) of the PAF antagonist phomactin A isolated from the marine fungus Phoma sp. The same bicyclo[9.3.1]pentadecane ring system 24 could also be produced by treatment of the polyene 23 with Grubbs' ruthenium catalyst in hot CH2Cl2 for 10 h (∼ 30%).

  用 CrCl2-NiCl2 在二甲基亚砜中处理醛乙烯基碘化物 17、19 a 和 19 b，可使它们大环化，分别生成从海洋真菌 Phoma sp.中分离出来的 PAF 拮抗剂 phomactin A 的含氧环系统 18、20 和 21（43-63%）。同样的双环[9.3.1]十五烷环系统 24 也可以通过在热 CH2Cl2 中用 Grubbs 的钌催化剂处理聚烯 23 10 小时而生成（30%∼）。
• A versatile and selective route to difunctional trisubstituted (E)-alkene synthons via zirconium-catalyzed carboalumination of alkynes
  作者：Cynthia L. Rand、David E. Van Horn、Mark W. Moore、Eiichi Negishi

  DOI：10.1021/jo00333a041

  日期：1981.9
• Efficient Assembly of the Phomactin Core via Two Different Macrocyclization Protocols
  作者：Tom J. Houghton、Soongyu Choi、Viresh H. Rawal

  DOI：10.1021/ol0163833

  日期：2001.11.1

  [GRAPHICS]The core structure of phomactins C and D was assembled by an efficient strategy starting from 3,4-dimethylcyclohexen-2-one. Key reactions include (1) a high yielding and highly diastereoselective Michael addition of a mixed cuprate, (2) a carbonylative alkyne-enoltriflate coupling or an intramolecular addition of an acetylide onto an aldehyde to form the macrocycle, (3) chemoselective Michael addition of a cuprate to an enynone, to give the carbon framework of desformyl phomactin C or D, and finally (4) regioselective addition of a thia-nucleophile to the more reactive beta -position of the resulting dienone.