(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)benzene | 93768-83-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)benzene
• 英文别名: phenyltetramethyl cyclopentadiene
• CAS: 93768-83-3
• 化学式: C₁₅H₁₈
• 分子量: 198.308
• InChiKey: CQBXFXWAJFNRHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  氯化铑(三水) 、 (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)benzene 以 甲醇 为溶剂， 以71%的产率得到dichloro(tetramethylcyclopentadienylbenzene)rhodium(III)dimer
  参考文献：
  名称：

  Mechanistic Insights into an Unprecedented C−C Bond Activation on a Rh/Ga Bimetallic Complex:  A Combined Experimental/Computational Approach

  摘要：

  The unusual rearrangement of [RhCp*(GaCp*)(CH3)(2)] (1c) to [RhCp*(C5Me4Ga(CH3)(3))] (2) is presented and its mechanism is discussed in detail. C-13 MAS NMR spectroscopy revealed that the title reaction proceeds cleanly not only in solution but also in solid state, which supports a unimolecular reaction pathway. On the basis of H-1, C-13, and ROESY NMR spectroscopy as well as isolation and structural elucidation of the hydrolysis product, the compound [RhCp*(endo-eta(4)-C5Me5GaMe2)] (3a) was identified as a crucial reaction intermediate. DFT calculations on the B3LYP level of theory support this assignment and suggest a concerted C-C bond activation mechanism that topologically takes place at the gallium center. Furthermore, two fluxional processes of the reaction intermediate 3a were studied experimentally as well as by computational methods. First, a mechanism takes place similar to a ring-slipping process that exchanges a GaMe2 group between adjacent ring carbon atoms within the same Cp* ring. This process proceeds at a rate comparable to the NMR time scale and indeed is calculated to be energetically very favorable. Second, a unimolecular exchange process of the GaMe2 group between the two Cp* rings of 3a could be experimentally proven by the introduction of phenyl substituents as a label into the Cp* ligands at both sites, the rhodium as well as the gallium center. A series of experiments including deuteration studies and competition reactions was performed to substantiate the suggested mechanism being in accordance with DFT calculations on possible transition states.

  DOI：

  10.1021/ja055298d
• 作为产物：
  描述：

  2,3,4,5-tetramethyl-1-phenylcyclopent-2-en-1-ol 在 盐酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 1.0h， 以2.064 g的产率得到(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)benzene
  参考文献：
  名称：

  Extending the range of pentasubstituted cyclopentadienyl compounds: The synthesis of a series of tetramethyl(alkyl or aryl)cyclopentadienes (Cp ∗ R ), their iridium complexes and their catalytic activity for asymmetric transfer hydrogenation

  摘要：

  Tetramethyl(alky or aryl)cyclopentadienes were synthesized and the organometallic half-sandwich iridium complexes of the form [(eta(5)-Cp*(R))Ir(aa)Cl], Cp*(R) = tetramethyl(phenyl)cyclopentadienyl (Cp*(Ph)), tetramethyl(benzyl)cyclopentadienyl (Cp*(Bn)), tetramethyl(2-propyl)cyclopentadienyl (Cp*(iPr)), or tetramethyl(cyclohexyl)cyclopentadienyl (Cp*(Cy)) were prepared and characterized. The complexes adopt a piano stool configuration, forming diastereomers, with ratios similar to reported [(eta(5)-Cp*(R))Ir(aa)Cl] complexes. The complexes display an intermolecular hydrogen bonding network in the solid state. These complexes were tested for the asymmetric transfer hydrogenation of several ketones, showing that the R of the Cp*(R) drastically impacts both selectivity and rate of reaction. Additionally, severe solvent effects are displayed when the reaction media is changed from aqueous to organic solvent. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2014.06.053

文献信息

• Half-sandwich iridium N-heterocyclic carbene anticancer complexes
  作者：Chuanlan Wang、Jinfeng Liu、Zhenzhen Tian、Meng Tian、Laijin Tian、Wenqian Zhao、Zhe Liu

  DOI：10.1039/c7dt00575j

  日期：——

  enyl IrIII complexes of the type [(η5-Cpx)Ir(C^C)Cl]PF6, where Cpx is pentamethylcyclopentadienyl (Cp*), or its phenyl (Cpxph = C5Me4C6H5) or biphenyl (Cpxbiph = C5Me4C6H4C6H5) derivatives, and the C^C-chelating ligands are different N-heterocyclic carbene (NHC) ligands, have been synthesized and characterized. Three X-ray crystal structures have been determined. Except for Cp* complex 1A, the other

  半夹心伪八面体的Ir五甲基环戊二烯III的类型的配合物[（η 5 -CP X）IR（C ^ C）CL] PF 6，其中CP X是五甲基环戊二烯（CP *），或它的苯基（CP XPH = C 5 Me 4 C 6 H 5）或联苯（CP xbiph = C 5 Me 4 C 6 H 4 C 6 H 5）衍生物，并且C ^ C螯合配体是不同的N-杂环卡宾（NHC）配体，已经合成并表征。已经确定了三种X射线晶体结构。除CP *复合物1A外，其他11种复合物1B–4C均显示出有效的细胞毒性，对HeLa人宫颈癌细胞的IC 50值范围为2.9至46.3μM。对HeLa细胞的效力随着CP *上其他苯基的取代而增加：CP xbiph > CP xph > CP *，并随着C ^ C-配体上链取代的大小增加，顺序为：ph>丁基>乙基>甲基。配合物[（η 5 -C 5我4 Ç 6 ħ4 C 6 H 5）Ir（L4）Cl]
• Fluorescent iridium(<scp>iii</scp>) coumarin-salicylaldehyde Schiff base compounds as lysosome-targeted antitumor agents
  作者：Cong Liu、Xicheng Liu、Xingxing Ge、Qinghui Wang、Lei Zhang、Wenjing Shang、Yue Zhang、Xiang Ai Yuan、Laijin Tian、Zhe Liu、Jinmao You

  DOI：10.1039/d0dt00627k

  日期：——

  coefficient: ∼0.7), damaged the integrity of the lysosomes, and induced apoptosis. The compounds could also decrease the mitochondrial membrane potential, catalyze the oxidation of the coenzyme (nicotinamide-adenine dinucleotide) and improve the levels of the intracellular reactive oxygen species, following an antitumor mechanism of oxidation. Additionally, these compounds could block the metastasis of tumor

  制备并表征了六种荧光半三明治铱（iii）香豆素-水杨醛席夫碱（O ^ N）化合物（[（η5-Cp*）Ir（O ^ N）Cl]。香豆素单元的引入增加了这些化合物的抗肿瘤活性（IC50：9.9±0.1μM-40.7±12.9μM），其中最好的抗癌活性几乎是临床顺铂的两倍。激光共聚焦显微镜的结果表明，这些化合物具有能量依赖性细胞摄取机制，积累在溶酶体中（Pearson共定位系数：〜0.7），破坏了溶酶体的完整性，并诱导了细胞凋亡。这些化合物还可以降低线粒体膜电位，催化辅酶（烟酰胺-腺嘌呤二核苷酸）的氧化并提高细胞内活性氧的含量，遵循抗氧化机制。另外，这些化合物可以阻断肿瘤细胞的转移。最重要的是，这些铱（iii）化合物显示出作为具有双重功能的抗肿瘤药的潜力：溶酶体损伤和抗转移。
• Modulating the water oxidation catalytic activity of iridium complexes by functionalizing the Cp*-ancillary ligand: hints on the nature of the active species
  作者：Giordano Gatto、Alice De Palo、Ana C. Carrasco、Ana M. Pizarro、Stefano Zacchini、Guido Pampaloni、Fabio Marchetti、Alceo Macchioni

  DOI：10.1039/d0cy02306j

  日期：——

  A comparative study on the behavior of a series of iridium dimeric WOCs with modified Cp* ligands reveals the key role played by the variable substituent.

  一项关于一系列具有改性Cp*配体的铱二聚WOCs行为的比较研究揭示了可变取代基发挥的关键作用。
• Alkyne Hydroamination and Trimerization with Titanium Bis(phenolate)pyridine Complexes: Evidence for Low-Valent Titanium Intermediates and Synthesis of an Ethylene Adduct of Titanium(II)
  作者：Ian A. Tonks、Josef C. Meier、John E. Bercaw

  DOI：10.1021/om400080g

  日期：2013.6.24

  class of titanium precatalysts of the type (ONO)TiX2 (ONO = pyridine-2,6-bis(4,6-di-tert-butylphenolate); X = Bn, NMe2) has been synthesized and crystallographically characterized. The (ONO)TiX2 (X = Bn, NMe2, X2 = NPh) complexes are highly active precatalysts for the hydroamination of internal alkynes with primary arylamines and some alkylamines. A class of titanium imido/ligand adducts, (ONO)Ti(L)(NR)

  已经合成了一类（ONO）TiX 2（ONO =吡啶-2,6-双（4,6-二叔丁基苯酚酸酯）； X = Bn，NMe 2）钛预催化剂，并进行了晶体学表征。（ONO）TiX 2（X = Bn，NMe 2，X 2 = NPh）配合物是高活性的预催化剂，用于内部炔烃与伯芳基胺和某些烷基胺的加氢胺化。一类钛亚氨基/配体加合物（ONO）Ti（L）（NR）（L = HNMe 2，py; R = Ph，t Bu）也已合成并表征，并据称为中间体提供了结构类似物催化循环。此外，这些配合物表现出不同寻常的氧化还原行为。（ONO）钛2（1）可能通过1的原位生成的具有催化活性的Ti II物种促进富电子炔烃的环三聚。根据反应条件，建议这些Ti II物质是通过Ti亚苄基或亚氨基中间体生成的。甲正式的Ti II复合物，（ONO）的Ti II（η 2 -C 2 H ^ 4）（HNME 2）（7），已经制备和结构表征。
• 一种半三明治结构铱二茂铁吡啶配合物及其制备方法和应用
  申请人：曲阜师范大学

  公开号：CN113754701A

  公开（公告）日：2021-12-07

  本发明公开了一种半三明治结构铱二茂铁吡啶配合物及其制备方法和抗癌应用。其结构式如式（I）所示，R为甲基、苯基或联苯基，双键为顺、反两种构型。通过测试目标配合物对人类肺泡基底上皮癌细胞、子宫颈癌细胞和人肺正常上皮细胞的生长抑制率，并对比发现目标配合物表现出良好的抗癌活性，证实了二茂铁与金属铱配合物的协同抗癌效果。取代基R由甲基→苯基→联苯基，配合物的活性有效提升，证实了提高配体的供电子能力有利于提高此类配合物的抗癌活性。另外，反式构型的配合物也表现出了更高的活性。目标配合物可以在A549细胞内的溶酶体内积累，并导致溶酶体损伤，从而导致癌细胞死亡。配合物在正常细胞和癌细胞之间表现出一定的选择性。