(R)-1-ruthenocenylethan-1-ol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-1-ruthenocenylethan-1-ol
• 英文别名: (R)-1-ruthenocenylethanol
• 化学式: C₁₂H₁₄ORu
• 分子量: 275.313
• InChiKey: FRNJVXMCQOLSHU-QYCVXMPOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.79
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-1-ruthenocenylethan-1-ol 在 acetic acid anhydride 、 N(C₂H₅)3 、 4-(dimethylamino)pyridine 作用下， 以 二氯甲烷 为溶剂， 生成 (R)-1-α-acetoxyethylruthenocene
  参考文献：
  名称：

  Optically Active Ruthenocenylbis(phosphines): New Efficient Chiral Phosphine Ligands for Catalytic Asymmetric Reactions

  摘要：

  New optically active ruthenocenylbis(phosphines) (R)-N,N-dimethyl-1-[(S)-1'2-bis(diphenylphosphino)-ruthenocenyl]propylamine [(R)-(S)-Et-BPPRA] (5a) and its ethylamine analog [(R)-(S)-BPPRA] (5b) were prepared by way of stereoselective lithiation of (R)-N,N-dimethyl-1-ruthenocenylalkylamines (4), which were obtained by the asymmetric ethylation or methylation (>96% ee) of ruthenocenecarboxaldehyde with the corresponding dialkylzincs in the presence of a catalytic amount of an optically active aminoalcohol 2 followed by stereoretentive amination of the resulting (R)-1-ruthenocenylalkanols (3). An X-ray diffraction study of the crystal structure of PdCl2[(R)-(S)-Et-BPPRA] (6a) revealed that the P-Pd-P bite angle of the ruthenocenylbis(phosphine) complex (100.47 degrees) is larger than that of the ferrocene analog and the phenyl rings on the phosphorus atoms are located closer to the chlorine ligand and palladium atom, suggesting that the ruthenocenylphosphines are more enantioselective chiral ligands for asymmetric reactions catalyzed by transition metal complexes. Actually, the ruthenocenylphosphines gave high enantioselectivity (higher than the ferrocene analog) in the palladium-catalyzed asymmetric silylation of allylic chlorides with 1,1-dichloro-1-phenyl-2,2,2-trimethyldisilane (PhCl(2)SiSiMe(3)) (up to 92% ee) and in the palladium-catalyzed cyclization of 2-butenylene dicarbonate with methyl acetylacetate forming a vinyldihydrofuran (up to 86% ee).

  DOI：

  10.1021/ja00089a011
• 作为产物：
  描述：

  acetylruthenocene 在 dimethyl sulfide borane 作用下， 以 四氢呋喃 为溶剂， 以97%的产率得到(R)-1-ruthenocenylethan-1-ol
  参考文献：
  名称：

  有机金属核苷类似物：茂金属原子对癌细胞系毒性的影响†

  摘要：

  报道了一种新的含有钌茂茂的手性有机金属核苷类似物，其中烷基胸腺嘧啶和烷基羟基连接在一个环戊二烯基环的相邻位置。描述了该茂金属衍生物和两种对照化合物的合成方法，以及通过循环伏安法和X射线晶体学对其进行表征的方法。它们在人胰腺癌细胞系（MIA-Pa-Ca-2）中的生物学活性显着低于先前报道的三种类似的二茂铁化合物，这表明金属茂金属原子（Fe或Ru）的选择起着至关重要的作用。确定这些核苷类似物的抗癌特性，这反过来表明与常规核苷类似物具有不同的作用方式。

  DOI：

  10.1039/c9dt04174e

文献信息

• Organometallic nucleoside analogues: effect of the metallocene metal atom on cancer cell line toxicity
  作者：Media K. Ismail、Katie A. Armstrong、Samantha L. Hodder、Sarah L. Horswell、Louise Male、Huy V. Nguyen、Edward A. Wilkinson、Nikolas J. Hodges、James H. R. Tucker

  DOI：10.1039/c9dt04174e

  日期：——

  pancreatic cancer cell line (MIA-Pa-Ca-2) were significantly lower than those of three previously reported analogous ferrocene compounds, indicating that the choice of metallocene metal atom (Fe or Ru) plays a pivotal role in determining the anticancer properties of these nucleoside analogues, which in turn suggests a different mode of action from that of a conventional nucleoside analogue.

  报道了一种新的含有钌茂茂的手性有机金属核苷类似物，其中烷基胸腺嘧啶和烷基羟基连接在一个环戊二烯基环的相邻位置。描述了该茂金属衍生物和两种对照化合物的合成方法，以及通过循环伏安法和X射线晶体学对其进行表征的方法。它们在人胰腺癌细胞系（MIA-Pa-Ca-2）中的生物学活性显着低于先前报道的三种类似的二茂铁化合物，这表明金属茂金属原子（Fe或Ru）的选择起着至关重要的作用。确定这些核苷类似物的抗癌特性，这反过来表明与常规核苷类似物具有不同的作用方式。
• Optically Active Ruthenocenylbis(phosphines): New Efficient Chiral Phosphine Ligands for Catalytic Asymmetric Reactions
  作者：Tamio Hayashi、Akira Ohno、Shi-jie Lu、Yonetatsu Matsumoto、Emiko Fukuyo、Kazunori Yanagi

  DOI：10.1021/ja00089a011

  日期：1994.5

  New optically active ruthenocenylbis(phosphines) (R)-N,N-dimethyl-1-[(S)-1'2-bis(diphenylphosphino)-ruthenocenyl]propylamine [(R)-(S)-Et-BPPRA] (5a) and its ethylamine analog [(R)-(S)-BPPRA] (5b) were prepared by way of stereoselective lithiation of (R)-N,N-dimethyl-1-ruthenocenylalkylamines (4), which were obtained by the asymmetric ethylation or methylation (>96% ee) of ruthenocenecarboxaldehyde with the corresponding dialkylzincs in the presence of a catalytic amount of an optically active aminoalcohol 2 followed by stereoretentive amination of the resulting (R)-1-ruthenocenylalkanols (3). An X-ray diffraction study of the crystal structure of PdCl2[(R)-(S)-Et-BPPRA] (6a) revealed that the P-Pd-P bite angle of the ruthenocenylbis(phosphine) complex (100.47 degrees) is larger than that of the ferrocene analog and the phenyl rings on the phosphorus atoms are located closer to the chlorine ligand and palladium atom, suggesting that the ruthenocenylphosphines are more enantioselective chiral ligands for asymmetric reactions catalyzed by transition metal complexes. Actually, the ruthenocenylphosphines gave high enantioselectivity (higher than the ferrocene analog) in the palladium-catalyzed asymmetric silylation of allylic chlorides with 1,1-dichloro-1-phenyl-2,2,2-trimethyldisilane (PhCl(2)SiSiMe(3)) (up to 92% ee) and in the palladium-catalyzed cyclization of 2-butenylene dicarbonate with methyl acetylacetate forming a vinyldihydrofuran (up to 86% ee).