rac-(2-bromoferrocenyl)methyl acetate | 259827-35-5

• 英文名称: rac-(2-bromoferrocenyl)methyl acetate
• 英文别名: (R(p))-[CpFe(C5H3(Br)CH2OAc)]；(-)-(Rp)-C5H5FeC5H3BrCH2OAc
• CAS: 259827-35-5；869715-16-2；867378-89-0
• 化学式: C₁₃H₁₃BrFeO₂
• 分子量: 336.996
• InChiKey: GBHVFADIFBLEKR-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：
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• 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-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
• 作为产物：
  描述：

  1-bromo-2-(N,N-dimethylaminomethyl)ferrocene 、 乙酸酐 在 Na₂CO₃ 作用下， 以 乙酸酐 为溶剂， 以83%的产率得到rac-(2-bromoferrocenyl)methyl acetate
  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

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。