dicubyl ketone

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: dicubyl ketone
• 英文别名: dicubylmethanone；Di(cuban-1-yl)methanone
• 化学式: C₁₇H₁₄O
• 分子量: 234.298
• InChiKey: YXZQKPUBWFQMQZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  dicubyl ketone 以52%的产率得到
  参考文献：
  名称：

  Eaton Philip E., Galoppini Elena, Gilardi Richard, J. Amer. Chem. Soc, 116 (1994) N 17, S 7588-7596

  摘要：

  DOI：
• 作为产物：
  描述：

  1-立方烷羧酸 、 cubyllithium 在 乙基溴化镁 作用下， 生成 dicubyl ketone
  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

• The cubane paradigm in bioactive molecule discovery: further scope, limitations and the cyclooctatetraene complement
  作者：Sevan D. Houston、Tyler Fahrenhorst-Jones、Hui Xing、Benjamin A. Chalmers、Melissa L. Sykes、Jeanette E. Stok、Clementina Farfan Soto、Jed M. Burns、Paul V. Bernhardt、James J. De Voss、Glen M. Boyle、Maree T. Smith、John Tsanaktsidis、G. Paul Savage、Vicky M. Avery、Craig M. Williams

  DOI：10.1039/c9ob01238a

  日期：——

  antibiotics (cefaclor, penicillin G) and antihistamine (diphenhydramine), a smooth muscle relaxant (alverine), an anaesthetic (ketamine), an agrochemical instecticide (triflumuron), an antiparasitic (benznidazole) and an anticancer agent (tamibarotene). This investigation highlights the scope and limitations of incorporating cubane into bioactive molecule discovery, both in terms of synthetic compatibility

  在广泛的研究中进一步探索了古巴苯环生物立体异构体范式，涵盖了广泛的药物和农用化学模板，其中包括抗生素（头孢克洛，青霉素G）和抗组胺药（苯海拉明），平滑肌松弛剂（金银花），麻醉剂（氯胺酮） ），农药杀虫剂（triflumuron），抗寄生虫药（苯并硝唑）和抗癌剂（他米巴罗汀）。这项研究从合成相容性和物理性质匹配两方面突出了将古巴人纳入生物活性分子发现的范围和局限性。在Chagas病抗寄生虫苯并硝唑的情况下，Cuban保持了生物等排作用，尽管在抗癌药（他米巴罗汀）方面活性较低。发现应用环辛酸酯（COT）（生物）基序补体相对于苯母体可优化苯硝唑，并在他米巴罗汀的情况下相对于古巴类似物具有增强的抗癌活性。像所有生物等排体，支架和生物基序一样，也存在局限性（例如合成实现），在此使用失败的示例对它们进行了特别强调。迄今为止，由我们小组准备的所有模板的摘要均经过了生物学评估，这强烈支持以下观点：古巴是生
• 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：——
• Alkynylcubanes as Precursors of Rigid-Rod Molecules and Alkynylcyclooctatetraenes
  作者：Philip E. Eaton、Elena Galoppini、Richard Gilardi

  DOI：10.1021/ja00096a016

  日期：1994.8

  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.