2-bromo-1-iodoferrocene | 1094756-57-6

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: 2-bromo-1-iodoferrocene
• 英文别名: 1-bromo-5-iodocyclopenta-1,3-diene;cyclopenta-1,3-diene;iron(2+)
• CAS: 1094756-57-6
• 化学式: C₁₀H₈BrFeI
• 分子量: 390.829
• InChiKey: VDVDSZNWWAFKRY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.18
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-N,N-dimethyl-1-ferrocenylethylamine 、 2-bromo-1-iodoferrocene 在 (2-methylpropyl)lithium 、 zinc dibromide 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 三(2-呋喃基)膦 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 反应 22.67h， 以78%的产率得到(R_Fc)-2′′-bromo-(S_Fc)-2-((R)-1-N,N-dimethylaminoethyl)-1,1′′-biferrocene
  参考文献：
  名称：

  基于二茂铁的二膦配体：Walphos类似物的合成和在不对称氢化中的应用。

  摘要：

  总共合成了四种基于双二茂铁的Walphos型配体，并在铑，钌和铱催化的烯烃和酮的氢化反应中进行了结构表征和测试。Negishi偶联条件允许从两个不相同和不外消旋的二茂铁片段（R）-1-（N，N-二甲基氨基）乙基二茂铁和（S Fc）-2-bromoiodoferrocene选择性非对映地建立这些二膦配体的二茂铁骨架。（S Fc）-2-溴碘二茂铁的分子结构，偶联产物，两个配体和两个配合物（[PdCl2（L）]和[RuCl（p-cymene）（L）] PF6）的结构由X-射线衍射。将配合物的结构特征和使用新合成的基于二茂铁的配体获得的催化结果与相应的Walphos配体进行了比较。

  DOI：

  10.1021/om3012147
• 作为产物：
  描述：

  1,2-二溴二茂铁 在 正丁基锂 、 碘 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 以98%的产率得到2-bromo-1-iodoferrocene
  参考文献：
  名称：

  1,2-二取代二茂铁的改进合成

  摘要：

  1,2-二取代的二茂铁，特别是1,2-二卤代二茂铁，是重要的原料。在此，我们描述了 1,2-二取代二茂铁（例如 1,2-二溴和 1,2-二碘二茂铁以及 1-溴-2-碘二茂铁和 1-溴-2-氟二茂铁）的显着改进的高产合成. DFT 计算表明，1,2-二卤二茂铁的最高占据分子轨道 (HOMO) 能量差异不大；然而，它们的最低未占分子轨道 (LUMO) 能量——因此是 HOMO/LUMO 间隙——与卤素电负性的总和相关。此外，还提出了一种相当敏感的 2-氨基二茂铁羧酸（邻氨基苯甲酸的二茂铁类似物）的合成，它从二茂铁-1,2-二羧酸开始。然而，2-氨基二茂铁羧酸迅速分解，因此无法正确表征。二茂铁-1,2-二羧酸酐用作初步光化学脱羰/脱羧实验的起始材料，当在[D8]甲苯中进行时产生1,2-二氘代二茂铁。

  DOI：

  10.1002/ejic.201600766

文献信息

• Disubstituted Ferrocenyl Iodo- and Chalcogenoalkynes as Chiral Halogen and Chalcogen Bond Donors
  作者：Victor Mamane、Paola Peluso、Emmanuel Aubert、Robin Weiss、Emmanuel Wenger、Sergio Cossu、Patrick Pale

  DOI：10.1021/acs.organomet.0c00633

  日期：2020.11.9

  by asymmetric synthesis. The XB donor property of racemic ferrocenyl iodoalkynes was demonstrated in solution in two benchmark reactions: the Ritter reaction and the benzoxazole synthesis from thioamides. In contrast, the ferrocenyl chalcogenoalkynes were far less active in these reactions. The potential of racemic and enantiopure ferrocenyl iodoalkynes as XB donors was also confirmed by X-ray diffraction

  基于卤素和硫族元素键（XB和ChB）的不对称催化仍处于起步阶段，寻找新的手性XB和ChB供体代表了其发展的关键一步。在这种情况下，我们设计并准备了包含三个关键子结构的新基序：即，以碘和硫属元素原子为中心的电子电荷密度耗尽区域，乙炔基官能度和平面手性二茂铁基平台。通过不对称合成将九个二茂铁基碘炔烃制备为纯对映体。外消旋二茂铁基碘炔的XB供体性质在溶液中通过两个基准反应得到证明：Ritter反应和硫代酰胺合成苯并恶唑。相反，二茂铁基硫属炔烃在这些反应中活性低得多。
• Deprotonative metallation of ferrocenes using mixed lithium–zinc and lithium–cadmium combinations
  作者：Gandrath Dayaker、Aare Sreeshailam、Floris Chevallier、Thierry Roisnel、Palakodety Radha Krishna、Florence Mongin

  DOI：10.1039/b924939g

  日期：——

  A mixed lithium–cadmium amide and a combination of lithium and zinc amides were reacted with a range of ferrocenes; deprotonative mono- or dimetallation in general occurred chemoselectively at room temperature, as evidenced by subsequent quenching with iodine.

  一种混合锂-镉酰胺与锂和锌酰胺的组合与一系列二茂铁进行反应；通常在室温下，通过随后用碘淬灭可以证明，发生了选择性的去质子化单金属化或双金属化反应。
• 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).
• Walphos versus Biferrocene-Based Walphos Analogues in the Asymmetric Hydrogenation of Alkenes and Ketones
  作者：Afrooz Zirakzadeh、Manuela A. Groß、Yaping Wang、Kurt Mereiter、Walter Weissensteiner

  DOI：10.1021/om401074a

  日期：2014.4.28

  Two representative Walphos analogues with an achiral 2,2 ''-biferrocenediyl backbone were synthesized. These diphosphine ligands were tested in the rhodium-catalyzed asymmetric hydrogenation of several alkenes and in the ruthenium-catalyzed hydrogenation of two ketones. The results were compared with those previously obtained on using biferrocene ligands with a C-2-symmetric 2,2 ''-biferrocenediyl backbone as well as with those obtained with Walphos ligands. The application of one newly synthesized ligand in the hydrogenation of 2-methylcinnamic acid gave (R)-2-methyl-3-phenylpropanoic acid with full conversion and with 92% ee. The same ligand was used to transform 2,4-pentanedione quantitatively and diastereoselectively into (S,S)-2,4-pentanediol with 98% ee.