1,1’-bis(di-o-tolylphosphino)ferrocene | 73881-42-2

• 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: 1,1’-bis(di-o-tolylphosphino)ferrocene
• 英文别名: 1,1'-bis(bis(o-tolyl)phopshino)ferrocene；1,1'-bis-[bis(2-methylphenyl)phosphino]ferrocene；cyclopenta-1,3-dien-1-yl-bis(2-methylphenyl)phosphane;iron(2+)
• CAS: 73881-42-2
• 化学式: C₃₈H₃₆FeP₂
• 分子量: 610.498
• InChiKey: LGDUFOOLXVALPY-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：

  二(氰基苯)二氯化钯 、 1,1’-bis(di-o-tolylphosphino)ferrocene 以 苯 为溶剂， 以74%的产率得到[1,1'-bis(bis(o-methylphenyl)phopshino)ferrocene]PdCl2
  参考文献：
  名称：

  茂金属桥联双齿双膦配体的钯配合物：胺化和交叉偶联反应的合成，结构和催化活性

  摘要：

  报道了一系列新的茂金属桥联的二膦的合成，表征以及其中一些与Pd（II）的配合物的结构。在卤代芳烃的胺化反应和Suzuki反应中，将这些配合物作为催化剂进行了研究。基于钌茂茂（2）和渗透茂（3）的配合物在胺化反应中的活性比具有dppf的钯配合物低，而在Suzuki反应中则具有相同的活性。新钯络合物与二齿笨重和富电子的配体的Fe（η 5 -C 5 H ^ 4 P（ø -Pr我Ç 6 ħ 4）2）2（6）和Fe（η 5 -C 5 H ^ 4 P（ø -MeOC 6 ħ 4）2）2（5）显示出非常高的催化在胺化和铃木活性芳基溴化物的耦合。与配体6的配合物被伯胺和仲胺用于4-溴甲苯的胺化反应，并显示出优异的活性。

  DOI：

  10.1021/om050869w
• 作为产物：
  描述：

  二茂铁 、 二-O-二甲苯氯化磷 在 LiC₄H₉, C₆H₁₆N₂ (TMEDA) 作用下， 以 正己烷 为溶剂， 以83%的产率得到1,1’-bis(di-o-tolylphosphino)ferrocene
  参考文献：
  名称：

  Palladium-Catalyzed Direct α-Arylation of Ketones. Rate Acceleration by Sterically Hindered Chelating Ligands and Reductive Elimination from a Transition Metal Enolate Complex

  摘要：

  DOI：

  10.1021/ja9727880

文献信息

• Evaluating 1,1′-Bis(phosphino)ferrocene Ancillary Ligand Variants in the Nickel-Catalyzed C–N Cross-Coupling of (Hetero)aryl Chlorides
  作者：Jillian S. K. Clark、Christopher N. Voth、Michael J. Ferguson、Mark Stradiotto

  DOI：10.1021/acs.organomet.6b00885

  日期：2017.2.13

  Previous reports in the literature have established the utility of 1,1'-bis(diphenylphosphino)ferrocene (DPPF, L-Ph) in the nickel-catalyzed cross-coupling of (hetero)aryl electrophiles with primary or secondary amines. In an effort to evaluate the effect of varying the PR2-donor groups On catalytic performance in such transformations, a series of 10 structurally varied 1,1'-bis(bis(alkyl/aryl)phosphino)ferrocene ancillary ligands (L-X) were systematically examined in selected competitive test cross couplings of (hetero)aryl halides with furfurylamine, morpholine, and indole employing Ni(COD)(2)/L-X catalyst mixtures. In addition to the excellent performance observed for the parent ligand LPh in a number of the test transformations explored, selected dialkylphosphino (e.g., DiPPF, L-iPr) and meta-disubstituted diarylphosphino variants of L-Ph also proved highly effective. In particular, the electron-deficient ligand variant L-CF3 featuring 3,5-bis(trifluoromethyl)phenyl groups on phosphorus was found to exhibit superior catalytic performance relative to L-Ph in most of the test transformations involving the N-arylation of indole. Our efforts to prepare Ni(II) precatalysts of the type (L-X)Ni(o-tolyl)Cl) in analogy with known (L-Ph)Ni(o-tolyl)Cl, by employing several literature methods met with mixed results. Whereas ((LNi)-Ni-iPr(o-tolyl)Cl was prepared straightforwardly and was crystallographically characterized, the use of L-CF3 or ligands featuring tert-butyl (L-tBu, o-tolyl (Lo-tol), or 4-methoxy-3,5dirnethylphenyl (L-OMe) groups on phosphorus under similar conditions resulted in poor conversion to product and/or the formation of poorly soluble materials, highlighting the limitations of this commonly used precatalyst design.
• Systematic Variation of Bidentate Ligands Used in Aryl Halide Amination. Unexpected Effects of Steric, Electronic, and Geometric Perturbations
  作者：Blake C. Hamann、John F. Hartwig

  DOI：10.1021/ja9721881

  日期：1998.4.1

  This paper presents effects of varying bidentate phosphine steric properties, electronic properties, and bite angle on product ratios in the amination of aryl bromides. Comparisons of the ratios of amine products to dehydrohalogenation products showed that catalysts containing electron rich, modestly hindered phosphines with small bite angles (similar to 90 degrees) gave the best selectivities. Surprisingly, the arene side product formed from reaction of alkylamines deuterated in the N-H position or deuterated in the position or to the nitrogen showed low levels of deuterium incorporation in many examples. Steric properties and ligand bite angle had the greatest impact on the selectivity for monoarylation versus diarylation of primary amines: ligands with small bite angles gave higher monoarylation-to-diarylation ratios, as did ligands with increased steric bulk. Electron poor or sterically hindered bidentate phosphines reduced the amount of product resulting from aryl exchange of electron rich palladium-bound arenes with those of aryl groups on the phosphine ligands.