rac-2-(hydroxymethyl)bromoferrocene | 146387-26-0

• 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: rac-2-(hydroxymethyl)bromoferrocene
• 英文别名: (2-bromocyclopenta-1,4-dien-1-yl)methanol;cyclopenta-1,3-diene;iron(2+)
• CAS: 146387-26-0；32824-44-5；12109-08-9
• 化学式: C₁₁H₁₁BrFeO
• 分子量: 294.959
• InChiKey: UDHHTGFIAGISEF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 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：

  rac-2-(hydroxymethyl)bromoferrocene 、 二苯基膦 在 chlorotrimethylsilane 、 NaI 作用下， 以 乙腈 为溶剂， 以90%的产率得到rac-2-[(diphenylphosphino)methyl]bromoferrocene
  参考文献：
  名称：

  Synthesis and structural characterization of rac-2-[(diphenylphosphino)methyl]ferrocenecarboxylic acid, its selected derivatives and some rhodium complexes

  摘要：

  rac-2-[(Diphenylphosphino)methyl]ferrocenecarboxylic acid (1) was prepared in a good yield from rac-2-(N,N-dimethylaminomethyl)bromoferrocene (2) via rac-2-(hydroxymethyl)bromoferrocene (4) and rac-2-[(diphenylphosphino)methyl]bromoferrocene (5), and further converted to the respective phosphine oxide (6), phosphine sulfide (7) and methyl ester (8). The phosphines 1 and 8 were studied as ligands in rhodium complexes. The reaction of di-mu-chloro-bis[chloro-(eta(5)-pentamethylcyclopentadienyl)rhodium(III)] with the stoichiometric amounts of 1 and 8 yielded the corresponding mononuclear complexes with P-monodentate ligands: [RhCl2,(eta(5)-C5Me5)(L-kappa P)], 9 and 10, respectively. Attempted deprotonation of 9 with LiBu or KOt-Bu gave intractable mixtures, in which the parent complex 9 as the major component was accompanied by two new compounds, likely the diastereoizomeric phosphinocarboxylate complexes. A defined O,P-chelating phosphinocarboxylate complex, [SP-4-2]-carbonyl-[rac-2-{(diphenylphosphino)methyl}ferrocenecarboxylato-kappa O-2,P]-tricyclohexylphosphinerhodium(I) (12), was obtained from the displacement of acetylacetonate(1-) (acac) ligand in [Rh(acac)(CO)(PCy3)] (Cy = cyclohexyl) with acid 1. The structures of 1, 6 - CHCl3, and 7 - 1/2CH(2)Cl(2), 10, and hydrated complexes 9 and 12 were determined by single-crystal X-ray diffraction. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.06.035
• 作为产物：
  描述：

  rac-(2-bromoferrocenyl)methyl acetate 以 not given 为溶剂， 以96%的产率得到rac-2-(hydroxymethyl)bromoferrocene
  参考文献：
  名称：

  溴化物介导的邻去质子化在手性，非外消旋二茂铁衍生物的合成中

  摘要：

  描述了由溴化物介导的1,2,3-和1,3-取代的二茂铁的合成方法。从单取代的二茂铁衍生物{Fc-R 1，R 1＝ 1-二甲基氨基乙基[CH（NMe 2）Me]，对甲苯基亚磺酰基[4-MeC 6 H 4 S（O）]，（2-甲氧基甲基吡咯烷-1-基）[2-MeOCH 2（C 4 H 7 N）CH 2 ]，麻黄碱衍生物CH 2 N（Me）CH（Me）CH（Ph）OMe和二甲基氨基甲基[CH 2（NMe 2）]}非手性，外消旋和手性的，非外消旋的1,2,3-三取代的二茂铁衍生物可通过两个连续的邻位锂化。在第一个去质子化步骤中，将溴化物立体选择性地引入位置2。在第二个步骤中，使用Li-TMP（TMP = 2,2,6,6-四甲基哌啶）作为碱会导致邻位的邻位去质子化溴化物，然后与不同的亲电试剂反应，得到各种1,2,3-三取代的二茂铁衍生物。除去中心溴化物取代基导致1，3-二取代的衍生物，包括钳型二茂铁配体。

  DOI：

  10.1021/om7003282

文献信息

• Stereoselective synthesis of chiral, non-racemic 1,2,3-tri- and 1,3-disubstituted ferrocene derivatives
  作者：Marianne Steurer、Karin Tiedl、Yaping Wang、Walter Weissensteiner

  DOI：10.1039/b508761a

  日期：——

  Chiral, non-racemic 1,2,3-trisubstituted ferrocene derivatives are accessible from monosubstituted ferrocenes through two sequential ortho-deprotonation reactions; removal of the central substituent gives 1,3-disubstituted ferrocenes.

  可通过两个顺序的邻位去质子化反应从单取代的二茂铁中获得手性，非外消旋的1,2,3-三取代的二茂铁衍生物。除去中心取代基得到1，3-二取代的二茂铁。
• The Chemistry of Phosphanyl‐ferrocenecarboxylic Ligands
  作者：Petr Štěpnička

  DOI：10.1002/ejic.200500485

  日期：2005.10

  AbstractThe chemistry of ferrocene attracts considerable research interest even more than 50 years after its discovery, being stimulated mainly by applications of ferrocene ligands in catalysis. To the present day, the design of new ferrocene compounds ensued—sometimes by serendipity—the preparation of unprecedented coordination compounds and organometallic materials and, in the case of ferrocene compounds containing appropriate donor sets, led to numerous successful catalytic systems. This review provides a systematic survey of the chemistry of phosphanyl‐ferrocenecarboxylic ligands as a specific class of hybrid ferrocene ligands that emerged about ten years ago, illustrating their synthesis, coordination behaviour, and catalytic applications. Attention is also paid to the structural chemistry of these functional ferrocene ligands. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)