1,1'-diiodoruthenocene | 70210-63-8

• 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: 1,1'-diiodoruthenocene
• 英文别名: 5-iodocyclopenta-1,3-diene;ruthenium(2+)
• CAS: 70210-63-8
• 化学式: C₁₀H₈I₂Ru
• 分子量: 483.053
• InChiKey: GJQOXDHUUXVKLK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1,1'-diiodoruthenocene 、 三甲基乙炔基硅 在 catalyst: mixt. of PdCl₂(PPh₃)2 and Cu(OAc)2*H₂O 作用下， 以 further solvent(s) 为溶剂， 以69%的产率得到1,1'-bis[(trimethylsilyl)ethynyl]ruthenocene
  参考文献：
  名称：

  Structure, Reactivity, and Electronic Properties of [4]Ferrocenophanes and [4]Ruthenocenophanes Prepared via a Novel Heteroannular Cyclization Reaction

  摘要：

  The reactions of 1,1'-bis((trimethylsilyl)ethynyl)ferrocene and 1,1'-bis((trimethylsilyl)-ethynyl)ruthenocene with catalytic quantities of alkali-metal methoxides in methanol directly afforded the highly unsaturated [4]metallocenophanes 1,1'-(1-methoxy-1,3-butadienylene)-ferrocene and 1,1'-(1-methoxy-1,3-butadienylene)ruthenocene, respectively, in high yields via a novel desilylation/heteroannular cyclization sequence. Analogously, 1,1'-bis((trimeth-ylsilyl)ethynyl)octamethylferrocene reacted to give 1,1'-(1-methoxy-1,3-butadienylene)oc-tamethylferrocene in high yield. The reactions of ((trimethylsilyl)ethynyl)ferrocene and ((trimethylsilyl)ethynyl)ruthenocene under identical conditions afforded ethynylferrocene and ethynylruthenocene, respectively. Synthetic elaboration of the heteroannular bridge of the cyclization products provided a route to additional [4]metallocenophanes. Treatment of 1,1'-(1-methoxy-1,3-butadienylene)ferrocene with acidic silica gel afforded 1,1'-(4-oxo-1-butenylene)ferrocene. Reaction of 1,1'-(4-oxo-1-butenylene)ferrocene with alane provided 1,1'-(1-butenylene)ferrocene, while reaction with sodium borohydride gave 1,1'-(4-hydroxy-1-butenylene)ferrocene. Dehydration of 1,1'-(4-hydroxy-1-butenylene)ferrocene on activated alumina provided 1,1'-(1,3-butadienylene)ferrocene. Similar synthetic transformations were carried out to yield the analogous series of ruthenocenophanes and octamethylferro-cenophanes. Voltammetric half-wave oxidation potentials were measured for all of the metallocenophanes in order to evaluate the electronic effect of the heteroannular bridges. X-ray crystal structure analyses were carried out on 1-1'-(1-methoxy-1,3-butadienylene)-ferrocene and 1,1'-(1-methoxy-1,3-butadienylene)ruthenocene. 1,1'-(1-Methoxy-1,3-butadi-enylene)ferrocene, C15H14FeO, crystallized in the orthorhombic space group Pcnb with a = 26.997(5) angstrom, b = 5.981(2) angstrom, c = 28.962(3) angstrom, Z = 16, and R = 0.072. 1,1'-(1-Methoxy-1,3-butadienylene)ruthenocene, C15H14RuO, crystallized in the monoclinic C2/c space group with a = 20.590(3) angstrom, b = 9.023(2) angstrom, c = 13.940(2) angstrom, 111.296(8)-degrees, Z = 8, and R = 0.021.

  DOI：

  10.1021/om00020a026
• 作为产物：
  描述：

  二茂钌 在 potassium tert-butylate 、 叔丁基锂 、 碘 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 25.0h， 以49%的产率得到iodoruthenocene
  参考文献：
  名称：

  Novel, Mercury-Free Synthetic Pathway for Trifluoromethylthio-Substituted Metallocenes

  摘要：

  A novel synthetic pathway for trifluoromethylthioferrocene (3), which does not involve the use of toxic mercury(II)-based reagents, is described. The novel approach involves first the treatment of the commercially available bromoferrocene (la) with NaSCN in the presence of copper(+I) to yield thiocyanatoferrocene (1), and then the reaction of 1 with the Rupper-Prakash reagent and tetrabutylammonium fluoride (TBAF) to give 3 in an overall yield of 60%. This approach could be extended for the preparation of thiocyanato-(4) and trifluoromethylthio-ruthenocene (7), which are herein both reported for the first time. Interestingly, diferrocenyl disulfide (2a) and diruthenocenyl disulfide (5) could be isolated as side-products during the synthesis of 3 and 7, respectively. All new compounds were unambiguously characterized by H-1, C-13, and F-19 NMR spectroscopy, mass spectrometry, cyclic voltammetry, elemental analysis, as well by X-ray crystallography for 1, 4, 4b, 5, 6, and 7.1-7 were further tested for their toxic activity on cervical cancer (HeLa) and noncancerous (MRC-5) cell lines. All organometallic compounds were found either to be nontoxic or to have a moderate toxicity toward the cell lines used in this study.

  DOI：

  10.1021/ic403169z

文献信息

• Synthesis and Biological Evaluation of Metallocene-Tethered Peptidyl Inhibitors of CDC25
  作者：Saonli Roy、Loganathan Rangasamy、Assia Nouar、Christiane Koenig、Vanessa Pierroz、Simon Kaeppeli、Stefano Ferrari、Malay Patra、Gilles Gasser

  DOI：10.1021/acs.organomet.1c00345

  日期：2021.8.9

  Using the pioneering concept developed by Jaouen, Brocard, and co-workers on the replacement of an organic moiety of a known drug by a ferrocenyl unit, we developed organometallic-containing peptides as inhibitors of dual-specificity phosphatases, cell division cycle 25 (CDC25). More precisely, we designed and prepared the first organometallic-containing CDC25 inhibitors based on the lead structure

  使用 Jaouen、Brocard 和同事开发的关于用二茂铁单元替换已知药物的有机部分的开创性概念，我们开发了含有有机金属的肽作为双特异性磷酸酶抑制剂，细胞分裂周期 25 (CDC25 ）。更准确地说，我们基于有机五肽抑制剂的先导结构设计并制备了第一个含有有机金属的 CDC25 抑制剂。然后进行了广泛的（生物）化学研究。我们首先确定含二茂铁和 CpMn(CO) 3的化合物在水性介质中不稳定，而二茂铁和 CpRe(CO) 3衍生品表现出稳健的稳定性。发现所有肽基化合物以剂量依赖性方式有效抑制纯化的 CDC25 磷酸酶的酶活性，其中钌衍生物 ( 3 ) 是该系列中最有效的。低剂量3当对含有内源性和外源性补充 CDC25 的细胞提取物进行离体研究时，可以部分阻止 CDC25 介导的其生理靶标 CDK1 的去磷酸化。不幸的是，用于评估肽基抑制剂的整体细胞毒性以及对细胞周期扰动的特定影响（例如在取决于