(3-tert-butoxy-prop-1-ynyl)trimethylsilane | 33664-40-3

• 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-tert-butoxy-prop-1-ynyl)trimethylsilane
• 英文别名: 1-tert-butoxy-3-(trimethylsilyl)-2-propyne；1-tert-butoxy-3-(trimethylsilyl)prop-2-yne；3-tert.-Butoxy-1-trimethylsilyl-1-propin；Trimethyl-[3-[(2-methylpropan-2-yl)oxy]prop-1-ynyl]silane
• CAS: 33664-40-3
• 化学式: C₁₀H₂₀OSi
• 分子量: 184.354
• InChiKey: JOWYLFAYHBCQMD-UHFFFAOYSA-N

物化性质

• 沸点：
  190.0±13.0 °C(Predicted)
• 密度：
  0.841±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.68
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 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-tert-butoxy-prop-1-ynyl)trimethylsilane 在 正丁基锂 作用下， 反应 1.25h， 生成 2,3-dimethoxy-4-hydroxy-4-(1-tert-butoxy-3,3-bis(trimethylsilyl)-1,2-propadienyl)-2-cyclobuten-1-one
  参考文献：
  名称：

  o-Quinone Methides from 4-Allenylcyclobutenones:  Synthesis and Chemistry

  摘要：

  Selected 4-allenylcyclobutenones ring expand to the corresponding o-quinone methides upon thermolysis in refluxing toluene or benzene. These reactive intermediates were not isolated but trapped to give stable products. The reaction has synthetic potential as a route to highly-substituted phenols, benzofurans, and aryl analogs of hexahydrocannabinol. In addition, a unique rearrangement involving a methyl migration from silicon to carbon of selected 4-[3,3-bis(trimethylsilyl)-1,2-propadienyl]cyclobutenones to give 1,2-benzoxasilols is described. Finally, data are presented that show rapid rotation around the alkylidene bond of o-quinone methides at 30 degrees C and that 2-(1-methylethenyl)phenols are in equilibrium with the corresponding o-quinone methides.

  DOI：

  10.1021/jo951445m
• 作为产物：
  描述：

  三甲基氯硅烷 、 叔丁基炔丙基乙醚 在 正丁基锂 作用下， 生成 (3-tert-butoxy-prop-1-ynyl)trimethylsilane
  参考文献：
  名称：

  Reactivity of allylic dimetallic zinc reagents. 1

  摘要：

  Allylic 1,1-dimetallic species 2, prepared in situ from the propargylic ether 1, are multicoupling reagents. They were allowed to react in a one-pot maction, with a large variety of electrophiles E1-carbonyl compounds (acyl chlorides, aldehydes, ketones, phenyl isocyanate, methyl chloroformate), alkyl bromides, and an amino ether-and then E2-acidic water, iodine, aryl or vinyl iodide in the presence of palladium(0). The isolated yields, based on 1 (5 steps), are fair to good in most cases. The first attack (E1) always occurs on the carbon atom alpha to the oxygen; the second attack (E2) is regio- and stereoselective on the carbon atom a to the TMS moiety.

  DOI：

  10.1021/jo00051a042

文献信息

• Addition of Hetero Allenyl Copper Reagents to Aldehydes: Scope and Behavior
  作者：Emmanuel Vrancken、Nacira Alouane、Hélène Gérard、Pierre Mangeney

  DOI：10.1021/jo062344z

  日期：2007.3.1

  propargylic amines or ethers react with aldehydes to give regioselectively the corresponding anti-homopropargylic alcohols with a high level of diastereoselectivity. Such selectivity could be obtained independently of the nature of the heteroatom (amine or ethers) or the acetylenic substituents. Excellent selectivities can be reached regardless of the aldehydes used, remarkably also with vinylic or acetylenic

  衍生自炔丙基胺或醚的氰基丙酸酯与醛反应，以区域选择性地产生具有高非对映选择性的相应的抗同炔丙基醇。可以独立于杂原子（胺或醚）或炔属取代基的性质而获得这种选择性。无论使用哪种醛，都能达到极好的选择性，尤其对于乙烯基或炔属的醛。带有不同炔基取代基的铜酸盐的反应活性等级被确定为：SiMe 3> Ph>等 还发现在HMPA的存在下加成至醛的反应速率减慢，这突出了Li抗衡离子的关键作用。DFT计算表明，与不稳定的炔丙基异构体相比，速率和炔属取代基之间的关系与可能的金属向平衡无关，而与反应性烯丙基种类的稳定性有关。
• Préparation et utilisation de lithiens de mono- et disilanes alléniques fonctionnels
  作者：Richard Mantione、Yves Leroux

  DOI：10.1016/s0022-328x(00)87458-6

  日期：1971.8
• <i>o</i>-Quinone Methides from 4-Allenylcyclobutenones:  Synthesis and Chemistry
  作者：Meng Taing、Harold W. Moore

  DOI：10.1021/jo951445m

  日期：1996.1.1

  Selected 4-allenylcyclobutenones ring expand to the corresponding o-quinone methides upon thermolysis in refluxing toluene or benzene. These reactive intermediates were not isolated but trapped to give stable products. The reaction has synthetic potential as a route to highly-substituted phenols, benzofurans, and aryl analogs of hexahydrocannabinol. In addition, a unique rearrangement involving a methyl migration from silicon to carbon of selected 4-[3,3-bis(trimethylsilyl)-1,2-propadienyl]cyclobutenones to give 1,2-benzoxasilols is described. Finally, data are presented that show rapid rotation around the alkylidene bond of o-quinone methides at 30 degrees C and that 2-(1-methylethenyl)phenols are in equilibrium with the corresponding o-quinone methides.
• Reactivity of allylic dimetallic zinc reagents. 1
  作者：Lydie Labaudiniere、Jezia Hanaizi、Jean F. Normant

  DOI：10.1021/jo00051a042

  日期：1992.12

  Allylic 1,1-dimetallic species 2, prepared in situ from the propargylic ether 1, are multicoupling reagents. They were allowed to react in a one-pot maction, with a large variety of electrophiles E1-carbonyl compounds (acyl chlorides, aldehydes, ketones, phenyl isocyanate, methyl chloroformate), alkyl bromides, and an amino ether-and then E2-acidic water, iodine, aryl or vinyl iodide in the presence of palladium(0). The isolated yields, based on 1 (5 steps), are fair to good in most cases. The first attack (E1) always occurs on the carbon atom alpha to the oxygen; the second attack (E2) is regio- and stereoselective on the carbon atom a to the TMS moiety.