1-((trimethylsilyl)ethynyl)-4-ethynylcubane | 163332-98-7

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1-((trimethylsilyl)ethynyl)-4-ethynylcubane
• 英文别名: 2-(4-Ethynylcuban-1-yl)ethynyl-trimethylsilane
• CAS: 163332-98-7
• 化学式: C₁₅H₁₆Si
• 分子量: 224.378
• InChiKey: LEHYICCIAPTHPS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.24
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-((trimethylsilyl)ethynyl)-4-ethynylcubane 在 吡啶 、 氧气 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 copper(I) bromide 作用下， 以87%的产率得到1,4-bis((trimethylsilyl)ethynyl)cubyl-1,3-butadiyne
  参考文献：
  名称：

  Alkynylcubanes as Precursors of Rigid-Rod Molecules and Alkynylcyclooctatetraenes

  摘要：

  We have developed new methodology for the synthesis of alkynylcubanes and have used these compounds to make rigid-rod molecules constructed of cubane and acetylene subunits. Terminal and substituted alkynylcubanes 7a, 7b, 8a, 8b, 12a, and 12b were synthesized by n-BuLi-promoted elimination of halogen from 1,1-dibromovinylcubanes 6a, 6b, and 11, followed by quenching with electrophiles. Systems with one or two acetylenic units between two cubanes were also prepared: dicubylacetylene (15) was obtained via reaction of the lithium ylide of (trimethylsilyl)diazomethane with dicubyl ketone (14); 1,4-dicubyl-1,3-butadiyne (16) was made by oxidative dimerization of ethynylcubane (7a). Dimerizations and cross-coupling reactions of various 1,4-diethynylcubanes afforded longer rods, e.g., 1,4-bis-((trimethylsilyl)ethynyl)cubyl- 1,3-butadiyne (18) and 1-(4-((trimethylsilyl)ethynyl)cubyl)-4-cubyl-1,3-butadiyne (21). Rh(I)-promoted ring opening of the cubane subunit(s) of these compounds into the corresponding tricyclooctadiene followed by thermal rearrangement to the cyclooctatetraene was used to convert 7a, 8a, and 12a into the mono- and disubstituted alkynylcyclooctatetraenes 22a, 22b, and 23 and to take 15 and 16 into the alkynyl-bridged cyclooctatetraenes 24a and 24b, respectively. X-ray crystallographic analysis of 12a, 15, 16, and 18 revealed interesting details about their structures.

  DOI：

  10.1021/ja00096a016
• 作为产物：
  描述：

  1,4-双(羟甲基)立方烷 在 盐酸 、 正丁基锂 、 草酰氯 、 methyllithium lithium bromide 、 二甲基亚砜 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.41h， 生成 1-((trimethylsilyl)ethynyl)-4-ethynylcubane
  参考文献：
  名称：

  Alkynylcubanes as Precursors of Rigid-Rod Molecules and Alkynylcyclooctatetraenes

  摘要：

  We have developed new methodology for the synthesis of alkynylcubanes and have used these compounds to make rigid-rod molecules constructed of cubane and acetylene subunits. Terminal and substituted alkynylcubanes 7a, 7b, 8a, 8b, 12a, and 12b were synthesized by n-BuLi-promoted elimination of halogen from 1,1-dibromovinylcubanes 6a, 6b, and 11, followed by quenching with electrophiles. Systems with one or two acetylenic units between two cubanes were also prepared: dicubylacetylene (15) was obtained via reaction of the lithium ylide of (trimethylsilyl)diazomethane with dicubyl ketone (14); 1,4-dicubyl-1,3-butadiyne (16) was made by oxidative dimerization of ethynylcubane (7a). Dimerizations and cross-coupling reactions of various 1,4-diethynylcubanes afforded longer rods, e.g., 1,4-bis-((trimethylsilyl)ethynyl)cubyl- 1,3-butadiyne (18) and 1-(4-((trimethylsilyl)ethynyl)cubyl)-4-cubyl-1,3-butadiyne (21). Rh(I)-promoted ring opening of the cubane subunit(s) of these compounds into the corresponding tricyclooctadiene followed by thermal rearrangement to the cyclooctatetraene was used to convert 7a, 8a, and 12a into the mono- and disubstituted alkynylcyclooctatetraenes 22a, 22b, and 23 and to take 15 and 16 into the alkynyl-bridged cyclooctatetraenes 24a and 24b, respectively. X-ray crystallographic analysis of 12a, 15, 16, and 18 revealed interesting details about their structures.

  DOI：

  10.1021/ja00096a016

文献信息

• OrthoFRET in Diamantane FRET in Orthogonal Stiff Dyads; Diamond Restriction for Frozen Vibrations
  作者：Heinz Langhals、Christian Dietl、Jeremy Dahl、Robert Carlson、Yaw-Terng Chern、Peter Mayer

  DOI：10.1021/acs.joc.0c01184

  日期：2020.9.4

  Energy transfer proceeds in orthogonal dyads in contrast to Förster’s theory and cannot be prohibited even by rigid interconnecting cage compounds such as cubane or diamantane.

  与福斯特（Förster）的理论相反，能量传递以正交的方式进行，即使刚性连接的笼状化合物（如古巴或金刚烷）也不能阻止能量传递。
• Cubane Cross-Coupling and Cubane-Porphyrin Arrays
  作者：Stefan S. R. Bernhard、Gemma M. Locke、Shane Plunkett、Alina Meindl、Keith J. Flanagan、Mathias O. Senge

  DOI：10.1002/chem.201704344

  日期：2018.1.24

  Herein, an improved methodology for aryl‐cubane cross‐coupling is reported. The peculiarities of the cubane core and its behavior during cross‐coupling conditions were analyzed, while the versatility of this adapted Baran cross‐coupling methodology was demonstrated by the synthesis of various aryl‐cubane systems, including coupling products of cubanes and porphyrins. Furthermore, arm extension of alkynyl‐cubanes

  本文报道了一种改进的芳基-古巴交叉偶联方法。分析了古巴核的特殊性及其在交叉耦合条件下的行为，同时通过各种芳基-古巴体系的合成，包括古巴和卟啉的偶联产物，证明了这种适应性的Baran交叉耦合方法的多功能性。此外，还展示了Sonogashira反应对炔基-古巴酮的臂延伸，这显示了在钯催化剂存在下，古巴尼核心的稳定性的第一个证据。
• Eaton Philip E., Galoppini Elena, Gilardi Richard, J. Amer. Chem. Soc, 116 (1994) N 17, S 7588-7596
  作者：Eaton Philip E., Galoppini Elena, Gilardi Richard

  DOI：——

  日期：——