(S_p)-1-bromo-2-vinylferrocene | 216019-76-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S_p)-1-bromo-2-vinylferrocene
• 英文别名: (S)-CpFe(η⁵-C₅H₃-1-Br-2-CHO)；(pS)-2-bromoferrocenecarboxaldehyde；2-bromocyclopenta-2,4-diene-1-carbaldehyde;cyclopenta-1,3-diene;iron(2+)
• CAS: 216019-76-0
• 化学式: C₁₁H₉BrFeO
• 分子量: 292.943
• InChiKey: KSAOOJVHTWLIMJ-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：

  (S_p)-1-bromo-2-vinylferrocene 在 (1-重氮基-2-氧代丙基)膦酸二甲酯 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 18.0h， 以86%的产率得到(S_Fc)-1-bromo-2-ethynylferrocene
  参考文献：
  名称：

  二取代的二茂铁基碘和硫属炔烃作为手性卤素和硫属元素键的供体

  摘要：

  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。

  DOI：

  10.1021/acs.organomet.0c00633
• 作为产物：
  描述：

  1-bromo-2-(N,N-dimethylaminomethyl)ferrocene 在 manganese(IV) oxide 作用下， 以 甲苯 为溶剂， 反应 1.5h， 生成 (S_p)-1-bromo-2-vinylferrocene
  参考文献：
  名称：

  Peptide-catalyzed kinetic resolution of planar-chiral metallocenes

  摘要：

  使用树脂支持的肽催化剂对消旋平面手性金属茂基化合物进行动力学分辨，其中低分子量有机催化剂无效。

  DOI：

  10.1039/c4cc03266g

文献信息

• [EN] METALLOCENE-BASED CHIRAL PHOSPHINE OR ARSINE LIGANDS<br/>[FR] LIGANDS DE PHOSPHINE OU D'ARSINE CHIRAUX A BASE DE METALLOCENE
  申请人：STYLACATS LTD

  公开号：WO2005068477A1

  公开（公告）日：2005-07-28

  The present invention relates to metallocene-based phosphine ligands having chirality at phosphorus and at least one other element of chirality (planar chirality and/or chirality at carbon); and to the use of such ligands in asymmetric transformation reactions to generate high enantiomeric excesses of formed compounds. A method for the preparation of ligands according to the invention involving the conversion of the ortho-lithiated substituted metallocene to a phosphine chiral at phosphorus is also disclosed.

  本发明涉及基于茂金属的膦配体，其在磷和至少另一个元素（平面手性和/或碳手性）上具有手性，并且涉及在不对称转化反应中使用这种配体以生成形成的化合物的高对映体过量的用途。本发明揭示了一种根据本发明制备配体的方法，涉及将取代的基于齿金属的ortho-锂化物转化为在磷上手性的膦。
• Planar Chiral, Ferrocene-Stabilized Silicon Cations
  作者：Ruth K. Schmidt、Hendrik F. T. Klare、Roland Fröhlich、Martin Oestreich

  DOI：10.1002/chem.201504777

  日期：2016.4.4

  preparation of a series of planar chiral, ferrocenyl‐substituted hydrosilanes as precursors of ferrocene‐stabilized silicon cations is described. These molecules also feature stereogenicity at the silicon atom. The generation and 29Si NMR spectroscopic characterization of the corresponding silicon cations is reported, and problems arising from interactions of the electron‐deficient silicon atom and adjacent

  描述了一系列平面手性二茂铁基取代的氢硅烷作为二茂铁稳定的硅阳离子的前体的制备。这些分子在硅原子上还具有立体性。报告了相应硅阳离子的生成和29 Si NMR光谱表征，以及由于缺电子的硅原子与相邻C（sp 3）-H键或芳族π供体进行了讨论。通过将硅原子上的另一个取代基束缚在二茂铁骨架上，可以解决这些问题。所得到的环状结构还赋予构象刚度和空间位阻，使得通过完全非对映控制设定硅原子上的中心手性。然后在困难的Diels-Alder反应中测试了这些手性Lewis酸催化剂，但没有发现对映体诱导作用。
• Enantioselective Synthesis of Ferrocene‐ or Cymantrene‐Fused Planar‐Chiral Phospholes
  作者：Hao Hu、Wei‐Yi Wu、Tamotsu Takahashi、Kazuhiro Yoshida、Masamichi Ogasawara

  DOI：10.1002/ejic.201600875

  日期：2017.1.10

  Planar-chiral ferrocene-fused phosphole (S)-1a was prepared in an enantiomerically pure form by enantioselective transformation. The synthesis was started with Kagan's chiral ferrocenyl acetal (–)-2a, and bromo and (Z)-2-bromovinyl substituents were introduced at the 1- and 2-positions of the ferrocene platform in (S)-6a with controlling its planar chirality. The double Li/Br exchange on (S)-6a followed

  平面手性二茂铁稠合磷光体 (S)-1a 是通过对映选择性转化以对映体纯形式制备的。合成是从 Kagan 的手性二茂铁缩醛 (-)-2a 开始的，在 (S)-6a 中二茂铁平台的 1-和 2-位引入溴和 (Z)-2-溴乙烯基取代基，控制其平面手性。在 (S)-6a 上进行双 Li/Br 交换，然后与 PhPBr2 反应以极好的收率提供 (S)-1a。(S)-1a 的结构由 X 射线晶体学确定。平面手性 cymantrene 稠合磷 (S)-1b 也是通过类似的不对称转化制备的，从 Jaouen 的手性 cymantrenyl 乙缩醛 (+)-2b 开始。
• Diastereo- and Enantioselective Metathesis Dimerization/Kinetic Resolution of Racemic Planar-Chiral Vinylferrocenes
  作者：Koji Nishimoto、Haruka Taue、Takehito Ohji、Sayaka Funakoshi、Yasuhiro Ohki、Masamichi Ogasawara

  DOI：10.1021/acs.orglett.2c02888

  日期：2022.10.14

  Diastereo- and enantioselective kinetic resolution of racemic planar-chiral 1-R-2-vinylferrocenes (rac-1) was attained by the molybdenum-catalyzed asymmetric metathesis dimerization (AMD). Two sequential AMD reactions of rac-1a (R = Br) provided (E)-(S,S)-1,2-di(2-bromoferrocenyl)ethylene in >99% ee, which was converted to (S,S)-1,2-bis[(2-diphenylphosphino)ferrocenyl]ethane (S,S)-5. Planar-chiral

  外消旋平面手性 1 - R -2-乙烯基二茂铁 ( rac - 1 ) 的非对映和对映选择性动力学拆分是通过钼催化的不对称复分解二聚 (AMD) 实现的。rac - 1a (R = Br)的两个连续 AMD 反应提供了 ( E )-( S , S )-1,2-di(2-bromoferrocenyl)ethylene in >99% ee，它被转化为 ( S , S ) -1,2-双[(2-二苯基膦基)二茂铁基]乙烷 ( S , S )- 5。平面手性双膦 ( S , S )- 5以反式螯合方式与二氯钯 (II) 片段配位，在钯催化的不对称烯丙基烷基化反应中用作手性配体，显示出高达 90% ee 的对映选择性。
• 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).