(S)-ferrocenyl p-tolyl sulfoxide | 238753-24-7

• 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: (S)-ferrocenyl p-tolyl sulfoxide
• 英文别名: (Ss)-ferrocenyl p-tolylsulfoxide；(R)-Ferrocenyl p-Tolyl Sulfoxide；cyclopenta-1,3-diene;1-[(R)-cyclopenta-1,3-dien-1-ylsulfinyl]-4-methylbenzene;iron(2+)
• CAS: 238753-24-7
• 化学式: C₁₇H₁₆FeOS
• 分子量: 324.226
• InChiKey: QAAXXGKGRWQHLR-FMOMHUKBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.28
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-ferrocenyl p-tolyl sulfoxide 在 lithium diisopropyl amide 、 zinc dibromide 、 bis(acetylacetonate)nickel(II) 、 2-氯-2-苯基苯乙酮 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以60%的产率得到(pR,pR,S_S,S_S)-2,2″-bis(p-tolylsulfinyl)-1,1″-biferrocene
  参考文献：
  名称：

  Redox-Switchable Chiral Anions and Cations Based on Heteroatom-Fused Biferrocenes

  摘要：

  A new class of planar chiral heteroatom-bridged biferrocene species was prepared using (pR,pR,S-s,S-s)-2,2 ''-bis(p-tolylsulfinyl)-1,1 ''-biferrocene (pR,pR,S-s,S-s)-2 as a readily accessible precursor. Initially, one of the sulfinate groups in compound 2 is replaced with a trimethylstannyl or dimesitylboryl group. Replacement of the second sulfinate group with t-BuLi then results in cyclization to give the Me2Sn-bridged species (pS,pS)-4Sn and the Mes(2)B-bridged borate anion [(pS,pS)-4B](-). The products are redox active, as cyclic and square wave voltammetry data of (pS,pS)-4Sn and [Li(12-c-4)(2)] [(pS,pS)-4B] reveal two separate reversible oxidation events. events. The mixed-valent species [(pS,pS)-4Sn](+) and (pS,pS)-4B can also be obtained by chemical oxidation with AgPF6 or by simple exposure to air, respectively. A comparison of X-ray crystal structures reveals that the oxidized (mixed-valent) species contain distinct Fe(:1) and Fe(III) sites, but UV visible NIR spectra display IVCT bands at ca. 4000 and 5000 cm(-1), indicative of electronic coupling in solution. All compounds are obtained in enantiomerically pure form, suggesting potential use as switchable chiral anions and cations.

  DOI：

  10.1021/acs.organomet.5b00577
• 作为产物：
  描述：

  溴代二茂铁 、 (1R,2S,5R,SS)-(-)-menthyl p-toluenesulfinate 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.83h， 以67%的产率得到(S)-ferrocenyl p-tolyl sulfoxide
  参考文献：
  名称：

  平面手性叠氮基二茂铁的两种合成方法

  摘要：

  比较了合成手性叠氮基二茂铁（CAF）5和15的两种合成途径，手性叠氮二茂铁（CAFs）5和15是合成新的对映异构体富集的P，N-配体的关键中间体。第一种方法是基于卤化杂志与二茂铁的有机锌衍生物的钯催化交叉偶联反应（Negishi反应）。第二种方法采用了一种新的合成方法，该方法通过无卤（杂）芳烃与带有立体C和S原子的二茂铁锂的C-C偶联，通过芳族化合物的直接C-H功能化提供了一条较短的途径。P，N的钯配合物-配体已被用作Tsuji-Trost反应的催化剂，该反应以高对映选择性进行，以高收率得到烯丙基取代产物。

  DOI：

  10.1021/jo5014299

文献信息

• Ferrocenylindium Reagents in Palladium-Catalyzed Cross-Coupling Reactions: Asymmetric Synthesis of Planar Chiral 2-Aryl Oxazolyl and Sulfinyl Ferrocenes
  作者：Mauro Mato、Cristina Pérez-Caaveiro、Luis A. Sarandeses、José Pérez Sestelo

  DOI：10.1002/adsc.201601397

  日期：2017.4.17

  of ferrocenylindium species and palladium‐catalyzed cross‐coupling reactions for the synthesis of monosubstituted and planar chiral 1,2‐disubstituted ferrocenes is described. Triferrocenylindium reagents (Fc3In) are efficiently prepared in a one‐pot procedure from ferrocenes by lithiation and transmetallation to indium using InCl3. The palladium‐catalyzed cross‐coupling reactions of Fc3In (40 mol%)

  描述了二茂铁基铟物种的制备和钯催化的交叉偶联反应，用于合成单取代和平面手性1,2-二取代的二茂铁。一锅法有效地制备了二茂铁基铟试剂（Fc 3 In），方法是从二茂铁通过InCl 3进行锂化和金属过渡生成铟。钯催化的Fc 3交叉偶联反应在（40 mol％）与各种有机亲电子试剂（芳基，杂芳基，苄基，烯基和酰基卤）在THF中于80°C过夜，可以提供多种单取代的二茂铁，收率良好至极佳。这种方法允许立体选择合成平面手性2-芳基-1-恶唑基二茂铁和2-芳基-1-亚磺酰基二茂铁，这在不对称催化中很重要。
• Synthesis, coordination behaviour, structural features and use in asymmetric hydrogenations of bifep-type biferrocenes
  作者：Gustavo Espino、Li Xiao、Michael Puchberger、Kurt Mereiter、Felix Spindler、Blanca R. Manzano、Félix A. Jalón、Walter Weissensteiner

  DOI：10.1039/b816544k

  日期：——

  A protocol for the synthesis of C2- and C1-symmetric 2,2″-diarylphosphino-substituted biferrocenes (bifep-type ligands) is presented and the preparation of four representatives is described [(Sp,Sp)-2-R12P-2″- R22P-1,1″-biferrocene; 1 (bifep): R1 = R2 = Ph; 2: R1 = Ph, R2 = Cy; 3: R1 = R2 = 3,5-Me2C6H3; 4: R1 = 3,5-Me2−4-OMe-C6H2, R2 = 3,5-(CF3)2C6H3]. In addition, the synthesis of three palladium(II) complexes ([PdX2(L)], 10: L = 1, X = Cl; 11: L = 4, X = Cl; 12: L = 1, X = C6F5 and of four bifep ruthenium complexes (13: [RuCl(p-cymene)(1)]PF6; 14: [RuI(p-cymene)(1)]PF6; 15: [RuCl(benzene)(1)]PF6; 16: [RuI(p-cymene)(1)]I) is reported. In the solid state the biferrocene unit of complexes 10, 11 and 15 adopt either a (P)-shaped (10) or an (M)-shaped (11, 15) conformation. In solution, palladium complexes 10 and 11 are present as equilibrium mixtures of rapidly interconverting (P)- and (M)-shaped conformers. Rhodium- and iridium-mediated asymmetric hydrogenations of a number of olefins and one imine give products with only low to moderate enantiomeric excess, while in the ruthenium-catalyzed hydrogenation of ketones a maximum e.e. of 82% is obtained. The low enantioselectivities are assumed to be related to the conformational flexibility of bifep-type ligands.

  本文介绍了一种合成 C2- 和 C1-对称 2,2″-二芳基膦取代的双铁金属化合物（bifep型配体）的协议，并描述了四种代表性化合物的制备 [(Sp,Sp)-2-R12P-2″- R22P-1,1″-双铁金属化合物；1 (bifep): R1 = R2 = Ph; 2: R1 = Ph, R2 = Cy; 3: R1 = R2 = 3,5-Me2C6H3; 4: R1 = 3,5-Me2−4-OMe-C6H2, R2 = 3,5-(CF3)2C6H3]。此外，还报道了三种钯(II)配合物的合成（[PdX2(L)], 10: L = 1, X = Cl; 11: L = 4, X = Cl; 12: L = 1, X = C6F5）以及四种 bifep 钌配合物的合成（13: [RuCl(p-cymene)(1)]PF6; 14: [RuI(p-cymene)(1)]PF6; 15: [RuCl(benzene)(1)]PF6; 16: [RuI(p-cymene)(1)]I）。在固态下，配合物 10、11 和 15 的双铁金属单元采取 (P)-形（10）或 (M)-形（11、15）构象。在溶液中，钯配合物 10 和 11 以快速相互转换的 (P)- 和 (M)-形构象的平衡混合物存在。铑和铱催化的不对称氢化反应对多种烯烃和一种亚胺的产物具有较低至中等的光学纯度，而在钌催化的酮氢化反应中，最高 e.e. 为 82%。低选择性被认为是由于 bifep 型配体的构象灵活性所致。
• Synthesis and first application of a new family of monophosphine ferrocene ligands (MOPF)
  作者：Henriette L. Pedersen、Mogens Johannsen

  DOI：10.1039/a908921g

  日期：——

  A new family of monophosphine ferrocene ligands (MOPF) has been synthesised in two steps from an optically pure ferrocenyl sulfoxide and the first preliminary studies employing these ligands in asymmetric hydrosilylation of styrene are presented.

  一种新型的单膦基法拉第烯配体（MOPF）已由光学纯的法拉第烯基亚磺氧化物通过两步合成，并首次展示了使用这些配体进行苯乙烯不对称氢硅化反应的初步研究。
• Chiral Organoborane Lewis Pairs Derived from Pyridylferrocene
  作者：Jiawei Chen、Roger A. Lalancette、Frieder Jäkle

  DOI：10.1002/chem.201400057

  日期：2014.6.11

  In an effort to develop a new class of redox‐active chiral Lewis pairs, pyridine and borane moieties with different steric and electronic properties were introduced onto a planar chiral 1,2‐disubstituted ferrocene framework. Metathesis of lithiated, stannylated, or mercuriated pyridylferrocenes with boron halides afforded (pR)‐2‐[bis(pentafluorophenyl)boryl]‐1‐(3,5‐dimethylpyrid‐2‐yl)ferrocene (4‐Pf)

  为了开发新型的氧化还原活性手性路易斯对，将具有不同空间和电子特性的吡啶和硼烷部分引入了平面手性1,2-二取代的二茂铁骨架中。提供了卤化硼将锂化，锡烷基化或汞化的吡啶基二茂铁置换为（p R）-2-（双（五氟苯基）硼基）-1-（3,5-二甲基吡啶-2-基）二茂铁（4-Pf），（p [R）-2- [dimesitylboryl] -1-（3,5- dimethylpyrid -2-基）二茂铁（4-MES），（p小号）-2-（双（五氟苯基）硼）-1-（2- trimethylsilylpyrid -6-基）二茂铁（5-PF），或（对小号）-2- [dimesitylboryl] -1-（2- trimethylsilylpyrid -6-基）二茂铁（5-MES）。通过多核NMR光谱，HRMS和单晶X射线衍射分析了硼酸盐化的产物。手性HPLC和旋光度测量用于评估硼化过程的立体选择性并建立正确的立体化
• Facile axial chirality control by using a precursor with central chirality. Application to the preparation of new axially chiral diphosphine complexes for asymmetric catalysis
  作者：Matthias Lotz、Gernot Kramer、Paul Knochel

  DOI：10.1039/b207399d

  日期：2002.10.18

  A diastereoselective synthesis of a new chiral diphosphine with planar chirality is performed in 2 steps from (S)-p-tolylferrocenyl sulfoxide with 60% overall yield. The ligand gives enantioselectivities up to 98% ee in Pd(0)-catalyzed allylic substitution reactions.

  具有平面手性的新型手性二膦的非对映选择性合成从 (S)-p-tolyferrocenyl 亚砜分 2 步进行，总产率为 60%。在 Pd(0) 催化的烯丙基取代反应中，该配体提供高达 98% ee 的对映选择性。