1-bromo-2-(diphenylphosphino)ferrocene | 1094756-39-4

• 英文名称: 1-bromo-2-(diphenylphosphino)ferrocene
• 英文别名: 1-bromo-2-diphenylphosphinoferrocene
• CAS: 1094756-39-4
• 化学式: C₂₂H₁₈BrFeP
• 分子量: 449.11
• InChiKey: SYSACBQXCRXJML-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：

  1-bromo-2-(diphenylphosphino)ferrocene 、 N,N-二甲基甲酰胺 在 正丁基锂 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 2.0h， 以87%的产率得到1-(diphenylphosphino)-2-formylferrocene
  参考文献：
  名称：

  太阳辐射下二茂铁光解钌配合物中的膦富烯烯醇化配体

  摘要：

  已经通过光化学转化获得了含有新型膦配体的钌配合物。该过程包括用可见光（钨卤素灯）照射二茂铁基膦基-羰基钌衍生物，在“CpFe+”实体正式丢失后产生与 kappa2-P,O 膦基富烯-烯醇化物配体的配合物。串联反应也是可能的，其涉及二茂铁基羟基膦配体和钌芳烃前体的混合物的辐照。该反应通过羟基膦配体的配位、生成氢化酮（或氢化醛）配合物以及随后生成富烯衍生物而发生。该过程也发生在使用太阳辐射上。已经通过用 LED 照射在可见光谱的不同波长下研究了光解反应。当在对应于作为酰基二茂铁基部分特征的 MLCT 波段的波长范围内进行照射时，获得了积极的结果。使用绿光 (530 nm) 可获得最佳结果，并且在使用更高波长或在黑暗中不会发生反应。非配位的二茂铁基膦醛配体也在太阳辐射下产生，但得到了复杂的混合物，因此当存在钌中心时，选择性显着增加。使用绿光 (530 nm) 可获得最佳结果，并且在使用更高波长或

  DOI：

  10.1002/ejic.201601440
• 作为产物：
  描述：

  溴代二茂铁 、 二苯基氯化膦 在 2,2,6,6-tetramethylpiperidinyl-lithium 作用下， 以 四氢呋喃 为溶剂， 反应 22.0h， 以84%的产率得到1-bromo-2-(diphenylphosphino)ferrocene
  参考文献：
  名称：

  太阳辐射下二茂铁光解钌配合物中的膦富烯烯醇化配体

  摘要：

  已经通过光化学转化获得了含有新型膦配体的钌配合物。该过程包括用可见光（钨卤素灯）照射二茂铁基膦基-羰基钌衍生物，在“CpFe+”实体正式丢失后产生与 kappa2-P,O 膦基富烯-烯醇化物配体的配合物。串联反应也是可能的，其涉及二茂铁基羟基膦配体和钌芳烃前体的混合物的辐照。该反应通过羟基膦配体的配位、生成氢化酮（或氢化醛）配合物以及随后生成富烯衍生物而发生。该过程也发生在使用太阳辐射上。已经通过用 LED 照射在可见光谱的不同波长下研究了光解反应。当在对应于作为酰基二茂铁基部分特征的 MLCT 波段的波长范围内进行照射时，获得了积极的结果。使用绿光 (530 nm) 可获得最佳结果，并且在使用更高波长或在黑暗中不会发生反应。非配位的二茂铁基膦醛配体也在太阳辐射下产生，但得到了复杂的混合物，因此当存在钌中心时，选择性显着增加。使用绿光 (530 nm) 可获得最佳结果，并且在使用更高波长或

  DOI：

  10.1002/ejic.201601440

文献信息

• Halide-Mediated<i>Ortho</i>-Deprotonation Reactions Applied to the Synthesis of 1,2- and 1,3-Disubstituted Ferrocene Derivatives
  作者：Afrooz Zirakzadeh、Alexander Herlein、Manuela A. Groß、Kurt Mereiter、Yaping Wang、Walter Weissensteiner

  DOI：10.1021/acs.organomet.5b00464

  日期：2015.8.10

  The ortho-deprotonation of halide-substituted ferrocenes by treatment with lithium tetramethylpiperidide (LiTMP) has been investigated. Iodo-, bromo-, and chloro-substituted ferrocenes were easily deprotonated adjacent to the halide substituents. The synthetic applicability of this reaction was, however, limited by the fact that, depending on the temperature and the degree of halide substitution, scrambling of both iodo and bromo substituents at the ferrocene core took place. Iodoferrocenes could not be transformed selectively into ortho-substituted iodoferrocenes since, in the presence of LiTMP, the iodo substituents scrambled efficiently even at -78 degrees C, and this process had occurred before electrophiles had been added. Bromoferrocene and certain monobromo-substituted derivatives, however, could be efficiently ortho-deprotonated at low temperature and reacted with a number of electrophiles to afford 1,2- and 1,2,3-substituted ferrocene derivatives. For example, 2-bromo-1-iodoferrocene was synthesized by ortho-deprotonation of bromoferrocene and reaction with the electrophiles diiodoethane and diiodotetrafluoroethane, respectively. In this and related cases the iodide scrambling process and further product deprotonation due to the excess LiTMP could be suppressed efficiently by running the reaction at low temperature and in inverse mode. In contrast to the low-temperature process, at room temperature bromo substituents in bromoferrocenes scrambled in the presence of LiTMP. Chloro- and 1,2-dichloroferrocene could be ortho-deprotonated selectively, but in neither case was scrambling of a chloro substituent observed. As a further application of this ortho-deprotonation reaction, a route for the synthesis of 1,3-disubstituted ferrocenes was developed. 1,3-Diiodoferrocene was accessible from bromoferrocene in four steps. On a multigram scale an overall yield of 41% was achieved. 1,3-Diiodoferrocene was further transformed into symmetrically 1,3-disubstituted ferrocenes (1,3-R(2)Fc; R = CHO, COOEt, CN, CH=CH2).
• The conversion of 1,1′-dibromoferrocene to 1,2-dibromoferrocene: The ferrocene-chemist’s dream reaction
  作者：Ian R. Butler

  DOI：10.1016/j.inoche.2007.09.020

  日期：2008.1

  The conversion of 1,1'-dibromoferrocene to a range of 2-substituted bromoferrocenes is described. The products are useful in the preparation of a wide number of 1,2-disubstituted ferrocenes. This includes the preparation of 1,2-dibromoferrocene and 2-(diisopropylphosphino)bromoferrocene in what is a clean and simple synthesis. The synthesis may be carried out on a large scale and for the first time produces multigram quantities of these important precursor compounds. In addition the synthetic procedure may be modified to produce a new family of ferrocene-based tris-phosphine ligands such as bis(2-diphenylphosphinoferrocenyl)phenylphosphine. (c) 2007 Elsevier B.V. All rights reserved.