[CF₃]₈-DPPF | 70236-68-9

• 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: [CF₃]₈-DPPF
• 英文别名: bis[3,5-bis(trifluoromethyl)phenyl]-cyclopenta-2,4-dien-1-ylphosphane;iron(2+)
• CAS: 70236-68-9
• 化学式: C₄₂H₂₀F₂₄FeP₂
• 分子量: 1098.38
• InChiKey: OPFYBXZGYLLUSY-UHFFFAOYSA-N

物化性质

• 熔点：
  154-155°C

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：

  [CF₃]₈-DPPF 、 双三苯基膦二羰基镍 以 四氢呋喃 为溶剂， 以40%的产率得到dicarbonyl[1,1'-bis-[bis(3,5-bis(trifluoromethyl)phenyl)phosphino]ferrocene]nickel(0)
  参考文献：
  名称：

  Systematic Variation of Bidentate Ligands Used in Aryl Halide Amination. Unexpected Effects of Steric, Electronic, and Geometric Perturbations

  摘要：

  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.

  DOI：

  10.1021/ja9721881
• 作为产物：
  描述：

  1,1'-bis(dichlorophosphino)ferrocene 、 3,5-双三氟甲基溴苯 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 以74 %的产率得到[CF₃]₈-DPPF
  参考文献：
  名称：

  5-溴-1,2,3-三嗪的交叉偶联反应

  摘要：

  描述了 5-溴-1,2,3-三嗪的有效 Pd 催化交叉偶联方法。反应条件的优化允许制备具有代表性的（杂）芳基-1,2,3-三嗪（20 个实例，产率高达 97%）。使用支持硼酸化学空间的数据科学评估反应范围，以评估该方法的普遍性。此外，所得产品的多样化使得嘧啶和吡啶的制备收率高达 80%，并且只需两步即可完成。

  DOI：

  10.1021/acs.joc.2c02082
• 作为试剂：
  描述：

  4-乙烯基联苯 、 4-甲基乙酰苯胺 在 3,3-二甲基-1-丁烯 、 [CF₃]₈-DPPF 、 [Ir(cod)₂]OTf 作用下， 以 1,4-二氧六环 为溶剂， 反应 96.0h， 以49%的产率得到N-(2-(1-([1,1'-biphenyl]-4-yl)vinyl)-4-methylphenyl)acetamide
  参考文献：
  名称：

  通过双 CH 官能化，铱催化苯乙烯的 α-选择性芳基化。

  摘要：

  用二茂铁衍生的双膦配体修饰的 IrI 系统通过双 CH 官能化促进苯乙烯的 α-选择性芳基化。这些研究为 Pd 催化的 Fujiwara-Moritani 反应提供了一种区域异构替代方案。

  DOI：

  10.1002/anie.201808299

文献信息

• Rhodium‐Catalyzed Cyclization of Terminal and Internal Allenols: An Atom Economic and Highly Stereoselective Access Towards Tetrahydropyrans
  作者：Johannes P. Schmidt、Bernhard Breit

  DOI：10.1002/ange.202009166

  日期：2020.12.21

  AbstractA comprehensive study of a diastereoselective Rh‐catalyzed cyclization of terminal and internal allenols is reported. The methodology allows the atom economic and highly syn‐selective access to synthetically important 2,4‐disubstituted and 2,4,6‐trisubstituted tetrahydropyrans (THP). Furthermore, its utility and versatility are demonstrated by a great functional‐group compatibility and the

  摘要报道了末端和内部联烯醇的非对映选择性 Rh 催化环化的综合研究。该方法允许原子经济且高度顺‐选择性获得合成上重要的2,4-二取代和2,4,6-三取代四氢吡喃（THP）。此外，其良好的官能团兼容性和 (−)-centrolobine 的对映选择性全合成证明了其实用性和多功能性。
• Highly Active Platinum Catalysts for Nitrile and Cyanohydrin Hydration: Catalyst Design and Ligand Screening via High-Throughput Techniques
  作者：Xiangyou Xing、Chen Xu、Bo Chen、Chengcheng Li、Scott C. Virgil、Robert H. Grubbs

  DOI：10.1021/jacs.8b11667

  日期：2018.12.19

  Nitrile hydration provides access to amides that are indispensable to researchers in chemical and pharmaceutical industries. Prohibiting the use of this venerable reaction, however, are (1) the dearth of biphasic catalysts that can effectively hydrate nitriles at ambient temperatures with high turnover numbers and (2) the unsolved challenge of hydrating cyanohydrins. Herein, we report the design of

  腈水合为化学和制药行业的研究人员提供了必不可少的酰胺。然而，禁止使用这种古老的反应是 (1) 缺乏能够在环境温度下以高转换数有效水合腈类的双相催化剂，以及 (2) 水合氰醇的未解决挑战。在此，我们报告了通过精确地将富电子和缺电子配体相互反式排列，从而增强羟基的亲核性和腈基的亲电性来设计新型“供体-受体”型铂催化剂。利用高通量、自动化的工作流程并评估双齿配体库，我们发现了市售的廉价 DPPF [1,1' -ferrocenendiyl-bis(diphenylphosphine)] 提供优异的反应性。相应的“供体-受体”型催化剂2a很容易由(DPPF)PtCl2、PMe2OH和AgOTf制备。2a 的增强活性允许各种腈和氰醇在 40 °C 下以优异的转化率进行水合。对配体结构的合理重新评估导致发现了改性催化剂 2c，它含有更多富电子的 1,1'-双[双（5-甲基-2-呋喃基）膦基]二茂铁配体
• The Quest for the Ideal Base: Rational Design of a Nickel Precatalyst Enables Mild, Homogeneous C–N Cross-Coupling
  作者：Richard Y. Liu、Joseph M. Dennis、Stephen L. Buchwald

  DOI：10.1021/jacs.0c00286

  日期：2020.3.4

  Palladium-catalyzed amination reactions using soluble organic bases have provided a solution to the many issues associated with heterogeneous reaction conditions. Still, homogeneous C-N cross-coupling approaches cannot yet employ bases as weak and economical as trialkylamines. Furthermore, organic base-mediated methods have not been developed for Ni(0/II) catalysis, despite some advantages of such systems

  使用可溶性有机碱的钯催化胺化反应为与多相反应条件相关的许多问题提供了解决方案。尽管如此，均相 CN 交叉偶联方法尚不能使用与三烷基胺一样弱且经济的碱。此外，尽管有机碱介导的方法与类似的 Pd 基催化剂相比具有一些优势，但尚未开发出用于 Ni(0/II) 催化的有机碱介导方法。我们设计了一种新的空气稳定且易于制备的 Ni(II) 预催化剂，其带有缺电子的双齿膦配体，能够使用三乙胺 (TEA) 作为碱使芳基三氟甲磺酸酯与芳基胺交叉偶联。该方法可以容忍空间拥挤的偶联伙伴，以及带有碱和亲核试剂敏感官能团的偶联伙伴。借助密度泛函理论 (DFT) 计算，我们确定缺电子辅助配体降低了 Ni 键合胺的 pKa 和从所得 Ni(II)-酰胺络合物还原消除的障碍。此外，我们确定，由于空间因素，排除 Ni 催化剂和碱之间的路易斯酸碱络合对于避免催化剂抑制很重要。
• 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.