1-iodocubane-4-carboxaldehyde | 163332-88-5

• 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: 1-iodocubane-4-carboxaldehyde
• 英文别名: 4-Iodocubane-1-carbaldehyde
• CAS: 163332-88-5
• 化学式: C₉H₇IO
• 分子量: 258.058
• InChiKey: RAGIIMKIXCIMOB-UHFFFAOYSA-N

物化性质

• 熔点：
  106-109 °C
• 沸点：
  290.8±40.0 °C(Predicted)
• 密度：
  2.44±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  1-iodocubane-4-carboxaldehyde 以 甲苯 为溶剂， 反应 12.0h， 生成 苯甲酸苄酯
  参考文献：
  名称：

  Cage opening and rearrangement of 1-iodocubane-4-carboxaldehyde

  摘要：

  Cubane is a highly strained unsaturated molecule that was first synthesized in 1964 by Philip E. Eaton. Since cubane's discovery, it has been researched in pharmaceuticals, explosives, and polymers. Due to its range of uses, we have explored the thermo-stability of a number of cubane derivatives. Some derivatives have revealed its propensity to undergo cage opening/rearrangement. In examining 1-iodocubane-4-carboxaldehyde, we observed that benzoic acid, benzaldehyde, benzyl alcohol, and benzyl benzoate were surprisingly formed in this thermo-decay. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.09.037
• 作为产物：
  描述：

  4-碘卡宾羧酸 在 四丙基高钌酸铵 、 dimethyl sulfide borane 、 N-甲基吗啉氧化物 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 16.25h， 生成 1-iodocubane-4-carboxaldehyde
  参考文献：
  名称：

  通过古巴的价异构化环辛酸酯：范围和局限性

  摘要：

  在官能团耐受性，多重取代模式和古巴酒精经历一锅串联Ley-Griffith的能力的背景下，研究了伊顿铑（I）催化的古巴价氢异构化为环辛三烯（COT）的范围和局限性在没有过渡金属催化剂的情况下进行维蒂希反应。

  DOI：

  10.1002/chem.201805124

文献信息

• Nonclassical Phenyl Bioisosteres as Effective Replacements in a Series of Novel Open-Source Antimalarials
  作者：Edwin G. Tse、Sevan D. Houston、Craig M. Williams、G. Paul Savage、Louis M. Rendina、Irene Hallyburton、Mark Anderson、Raman Sharma、Gregory S. Walker、R. Scott Obach、Matthew H. Todd

  DOI：10.1021/acs.jmedchem.0c00746

  日期：2020.10.22

  The replacement of one chemical motif with another that is broadly similar is a common method in medicinal chemistry to modulate the physical and biological properties of a molecule (i.e., bioisosterism). In recent years, bioisosteres such as cubane and bicyclo[1.1.1]pentane (BCP) have been used as highly effective phenyl mimics. Herein, we show the successful incorporation of a range of phenyl bioisosteres

  一种化学基序被另一种广泛相似的基序替代是药物化学中调节分子的物理和生物学特性（即生物等排体）的常用方法。近年来，诸如古巴烯和双环[1.1.1]戊烷（BCP）等生物等排体已被用作高效的苯基模拟物。在本文中，我们显示了在抗疟疾系列的开源优化过程中成功结合了一系列苯基生物甾体。立方烷（19）和闭合碳-carborane（23）的类似物具有改进的体外针对效力恶性疟原虫与母体苯基化合物相比；然而，这些变化导致代谢稳定性降低；不寻常的是，发现酶介导的氧化作用发生在古巴核心。发现BCP类似物（22）与它的母体苯基化合物等价，并显示出明显改善的代谢特性。虽然这些结果证明了这些非典型生物等排体在药物化学程序中的用途，但寻找合适的生物等排体的搜索可能很可能需要制备许多候选化合物，在我们的情况下为32种化合物。
• Synthesis of a Novel Chiral Cubane-Based Schiff Base Ligand and Its Application in Asymmetric Nitro-Aldol (Henry) Reactions
  作者：Ronny Priefer、Michelle Ingalsbe、Jeffrey St. Denis、James Gleason、G. Savage

  DOI：10.1055/s-0029-1217083

  日期：2010.1

  cubane-based chiral Schiff base ligand has been successfully synthesized. This ligand has been evaluated on the nitro-aldol (Henry) reaction. The reactions were performed in the presence of four different copper salts, using eight different solvents, and five different temperatures. The highest enantioselectivity obtained for this novel ligand was ˜39% ee. cubane - aldol reactions - chirality - Schiff

  已成功合成了第一个报道的基于古巴的手性席夫碱配体。该配体已经在硝基-羟醛（亨利）反应上进行了评估。反应在四种不同的铜盐的存在下，使用八种不同的溶剂和五种不同的温度进行。对于该新型配体获得的最高对映选择性为〜39％ee。 古巴-Aldol反应-手性-Schiff碱-催化
• Thermochemical properties of iodinated cubane derivatives
  作者：Justin R. Griffiths、John Tsanaktsidis、G. Paul Savage、Ronny Priefer

  DOI：10.1016/j.tca.2009.10.015

  日期：2010.2

  Abstract Since the initial synthesis of cubane, numerous derivatives have been made with a diverse range of physical, chemical, and biological properties. Some iodinated cubane derivatives have been reported to be thermolytically unstable and/or rearrange in situ. An iodinated cubane-containing, norbornene-based polymer showed rapid thermo-decomposition during TGA studies. Bis-(4-iodocubylmethyl)-dialkoxy

  摘要 自古巴烷最初合成以来，已制备出许多具有各种物理、化学和生物特性的衍生物。据报道，一些碘化立方烷衍生物热解不稳定和/或原位重排。在 TGA 研究期间，含碘化立方烷的降冰片烯聚合物显示出快速热分解。双-(4-iodocubylmethyl)-二烷氧基二硫化物比其非碘化对应物更容易碎裂。本文报道了碘化立方烷化合物库的合成和热行为。大多数碘化立方烷衍生物在冷却时表现出熔化/分解，没有放热。在 DSC 分析过程中，观察到 4-Iodo-1-vinylcubane 重排为 4-vinyl-trans-β-iodo苯乙烯及其环辛四烯中间体。
• Evaluation of a chiral cubane-based Schiff base ligand in asymmetric catalysis reactions
  作者：Kyle F Biegasiewicz、Michelle L Ingalsbe、Jeffrey D St. Denis、James L Gleason、Junming Ho、Michelle L Coote、G Paul Savage、Ronny Priefer

  DOI：10.3762/bjoc.8.207

  日期：——

  Recently, a novel chiral cubane-based Schiff base ligand was reported to yield modest enantioselectivity in the Henry reaction. To further explore the utility of this ligand in other asymmetric organic transformations, we evaluated its stereoselectivity in cyclopropanation and Michael addition reactions. Although there was no increase in stereocontrol, upon computational evaluation using both M06L

  最近，据报道一种新的基于手性立方烷的希夫碱配体在亨利反应中产生适度的对映选择性。为了进一步探索该配体在其他不对称有机转化中的效用，我们评估了其在环丙烷化和迈克尔加成反应中的立体选择性。虽然立体控制没有增加，但在使用 M06L 和 B3LYP 计算进行计算评估时，发现存在伪六元环，通过立方氢与铜核的 H 键合。这减少了铜中心上方的空间体积并限制了该配体的不对称控制。
• 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.