bis(2-methyl-5-furyl)bromophosphine | 138136-24-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: bis(2-methyl-5-furyl)bromophosphine
• 英文别名: bromobis(5-methylfuran-2-yl)phosphine；bis(5-methyl-2-furyl)bromophosphine；bis(5-methyl-2-furyl)bromophosphane；Bromo-bis(5-methylfuran-2-yl)phosphane
• CAS: 138136-24-0
• 化学式: C₁₀H₁₀BrO₂P
• 分子量: 273.066
• InChiKey: RRIJZURGIVAURQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis(2-methyl-5-furyl)bromophosphine 以 正己烷 为溶剂， 反应 6.0h， 生成 O-ethyl bis(2-methyl-5-furyl)phosphinite
  参考文献：
  名称：

  Tolmachev, A. A.; Ivonin, S. P.; Kharchenko, A. V., Journal of general chemistry of the USSR, 1991, vol. 61, # 4.1, p. 778 - 782

  摘要：

  DOI：
• 作为产物：
  描述：

  2-甲基呋喃 在 吡啶 、 三溴化磷 作用下， 以16%的产率得到(2-methyl-5-furyl)dibromophosphine
  参考文献：
  名称：

  Tolmachev, A. A.; Ivonin, S. P.; Kharchenko, A. V., Journal of general chemistry of the USSR, 1991, vol. 61, # 4.1, p. 778 - 782

  摘要：

  DOI：

文献信息

• Congested Ferrocenyl Polyphosphanes Bearing Electron-Donating or Electron-Withdrawing Phosphanyl Groups: Assessment of Metallocene Conformation from NMR Spin Couplings and Use in Palladium-Catalyzed Chloroarenes Activation
  作者：Sophal Mom、Matthieu Beaupérin、David Roy、Sylviane Royer、Régine Amardeil、Hélène Cattey、Henri Doucet、J.-C. Hierso

  DOI：10.1021/ic2015379

  日期：2011.11.21

  4-chloropropiophenone, and 4-(trifluoromethyl)chlorobenzene were efficiently coupled to n-butyl furan, using Pd(OAc)2 associated to the new diphosphane ligands 1,1′-bis(diisopropylphosphanyl)-3,3′-di(triphenyl)methyl ferrocene (15) or 1,1′-bis(dicyclohexylphosphanyl)-3,3′-di(triphenyl)methylferrocene (16), which respectively hold the electron-rich −Pi-Pr2 and −PCy2 groups.

  报道了新的取代的环戊二烯基盐的合成，所述盐结合了稠合的支链烷基（叔丁基，（三苯基）甲基或三（4-叔丁基）苯基甲基）和膦酰基。引入或者吸电子或给电子取代基（呋喃基，的异丙基，环己基，叔丁基）上P原子以高收率普遍实现。研究了由这些环戊二烯基盐的组合物模制二茂铁基聚膦酸酯的方法，导致形成新的三膦烷（表示为9 – 12）和二膦烷（表示为14 – 16）。）。即使存在富电子取代基，生成的膦对空气或湿气也不敏感。这套聚膦显示出不同的构象特征，这是根据其在溶液中的多核NMR表征以及代表性的三膦1,2-双（二苯基膦基）-1'-（二异氰酸酯）的X射线固态结构进行了讨论。丙基膦基）-3'-（三苯基）甲基-4-叔丁基二茂铁，11。尤其是，对于这类三膦，异环P原子之间存在一系列明显不同的非键合（“贯穿空间”，TS）自旋-自旋偶合常数，可以评估它们在溶液中的优选构象。该研究表明，尽管存在非常拥挤的叔丁基和三苯甲基，
• Donor-Stabilized Phosphenium Adducts as New Efficient and Immobilizing Ligands in Palladium-Catalyzed Alkynylation and Platinum-Catalyzed Hydrogenation in Ionic Liquids
  作者：Samer Saleh、Elie Fayad、Michèle Azouri、Jean-Cyrille Hierso、Jacques Andrieu、Michel Picquet

  DOI：10.1002/adsc.200900133

  日期：2009.7

  were tested in palladium‐catalyzed aryl alkynylation and in the platinum‐catalyzed selective hydrogenation of chloronitrobenzenes, both in an ionic liquid phase. In CC bond cross‐coupling we observed that the increase of the π‐acceptor character in ligand 3d, due to the introduction of an additional electron‐withdrawing group, provides a very efficient catalyst in the alkynylation reaction of aryl bromides

  描述了通过将溴代呋喃基膦加到1,3-二甲基咪唑-2-羧酸酯1中来直接合成新的供体稳定的d配体3d。所获得的配体表现出非常强的π受体特性，与亚磷酸三苯酯[P（OPh）3 ]或三卤代膦的π受体特性相当，其三羰基镍配合物的v CO（A 1）在2087 cm -1。在离子液相中，在钯催化的芳基炔基化反应和铂催化的氯硝基苯选择性加氢反应中测试了该配体以及从氯二苯膦获得的相关3a。在CC键交叉耦合我们观察到，由于引入了另一个吸电子基团，配体3d中π受体特性的增加为芳基溴化物与苯乙炔的炔基化反应（包括失活的）提供了非常有效的催化剂。 4-溴茴香醚或位阻2-溴萘。由于配体对离子相中质子化的敏感性，催化活性随再循环而降低。相反，通过铂催化的间氯硝基苯加氢，可以在非酸性介质中实现金属/配体系统的多次循环。通过使用氯化铂（II）与3a [反式-PtCl 2的配合物]获得的催化结果（3a）2 ]与非离子相关的反
• Diastereoselective Synthesis of Dialkylated Bis(phosphino)ferrocenes: Their Use in Promoting Silver‐Mediated Nucleophilic Fluorination of Chloroquinolines
  作者：Julien Roger、Sylviane Royer、Hélène Cattey、Aleksandr Savateev、Radomyr V. Smaliy、Aleksandr N. Kostyuk、Jean‐Cyrille Hierso

  DOI：10.1002/ejic.201600502

  日期：2017.1.10

  and trimethylsilyl, has a significant influence on the stereoselectivity of the ensuing lithiation/phosphination reactions. Only the introduction of the tert-butyl groups ensures both a high yield and perfect diastereoselectivity, which leads to the exclusive formation of the rac planar chiral tert-butylated diphosphanes. The introduction of electron-rich and -poor phosphorus-based functional groups

  报道了在膦基上带有芳基、烷基和杂环或多环取代基的二烷基化二茂铁基双（膦）的非对映选择性合成，以及它们在固态下的 X 射线结构分析和溶液中的多核 NMR 光谱表征. 在二茂铁主链上引入各种烷基，即叔丁基、异丙基和三甲基甲硅烷基，对随后的锂化/膦化反应的立体选择性有显着影响。只有引入叔丁基才能确保高产率和完美的非对映选择性，从而导致外消旋平面手性叔丁基化二膦的独家形成。引入富电子和贫磷基官能团，即呋喃基-、异丙基-、环己基-、苯基-、实现了间甲基膦基和苯并膦吲哚，并以中等至高产率得到新的烷基化二茂铁基二膦。进行了研究以将这些强大的烷基化二膦作为助剂应用于非常具有挑战性的钯催化的氯喹啉在 C-Cl 键上的亲核氟化。出乎意料的是，二茂铁基膦的显着有利影响是通过使用商业 AgF 试剂进行这种氟化而证明的，这使得任何钯添加都无用。因此，这种创新的亲核氟化避免了苛刻的条件（严格无水）和高度专业化的试剂。
• Unsymmetrically Substituted Bis(phosphino)Ferrocenes Triggering Through-Space³¹(P, P′)-Nuclear Spin Couplings and Encapsulating Coinage Metal Cations
  作者：Tuan-Anh Nguyen、Marie-José Penouilh、Hélène Cattey、Nadine Pirio、Paul Fleurat-Lessard、Jean-Cyrille Hierso、Julien Roger

  DOI：10.1021/acs.organomet.1c00465

  日期：2021.11.8

  multinuclear NMR in solution, evidence that the strong SSCCs are attributable to the conformational constraint which is imposed to the ferrocene backbone by the introduction of alkyl substituents on this platform. The molecular structures resolved in the solid state showed long P···P mutual separation up to 6.9168(8) Å, while in solution, a (P, P′)-phosphorus lone-pair overlap clearly occurs. This testifies

  我们描述了非对称取代的二-叔-butylated 1,1'-双（膦基）二茂铁，用膦取代基R = [5-甲基] -2-呋喃基=赋，和R'=苯基（图4a），我-丙基（4b )。从二叔丁基化二茂铁平台 ( 1 )应用模块化合成方法，通过使用 1,1'-双（二碘）-3,3'-双（叔丁基）导致形成新的二膦二茂铁 ( 2 ) 作为合成前体。与迄今为止报道的表亲非烷基化不对称取代的二膦基二茂铁相比，这些二膦表现出很强的（31P, P')-非键合（“穿过空间”）核自旋-自旋耦合。这种核间自旋-自旋耦合常数 (SSCC) J PP'的强度范围在 17 到 35 Hz 之间，因此，它们与传统的“通过键” 4 J PP无关. 通过固态 X 射线衍射和溶液中的多核 NMR 表征这些二茂铁衍生物，证明强 SSCC 可归因于通过在该平台上引入烷基取代基而强加给二茂铁骨架的构象约束. 在固态下解析的分子结构显示长 P…P
• Converging and Diverging Synthetic Strategies to Tetradentate (<i>N</i>,<i>N</i>′)-Diaminomethyl,(<i>P</i>,<i>P</i>′)-Ferrocenyl Ligands: Influence of <i>tert</i>-Butyl Groups on Ferrocene Backbone Conformation
  作者：Fatima Allouch、Nejib Dwadnia、Nikolay V. Vologdin、Yurii V. Svyaschenko、Hélène Cattey、Marie-José Penouilh、Julien Roger、Daoud Naoufal、Ridha Ben Salem、Nadine Pirio、Jean-Cyrille Hierso

  DOI：10.1021/acs.organomet.5b00601

  日期：2015.10.26

  Hexasubstituted hybrid tetradentate (N,N',P,P')-ferrocenes bearing phosphino and aminomethyl groups, plus hindering tert-butyl moieties, were synthesized by using two different strategies: a "diverging" synthesis involving successive functionalization of preformed di-tert-butylated ferrocene and a "converging" assembly of the species from appropriately substituted cyclopentadienyl rings. While the new cydopentadienyl salts formed are of interest, their assembly with iron dichloride used as a "converging" way to produce tetradentate ferrocene ligands presented several drawbacks. Conversely, the synthesis of new tert-butylated (aminomethyl)ferrocene derivatives was found convenient to further form (N,N'-aminomethyl,(P,P'-tert-butylated-ferrocenyl diphosphines by N-directed ortho-metalation. The novel N-2-didentate and N2P2-tetradentate tert-butylated ferrocene compounds were all synthesized in good to high yields (48-96%) and tolerated aryl, alkyl, and heteroaryl phosphino groups as substituents on nitrogen and phosphorus atoms. They were characterized by X-ray diffraction and multinuclear NMR (H-1, C-13, P-31, N-15). We observed the conformation control provided to rac-(N,N'-diaminomethyl-(P,P'-tert-butylated-ferrocenyldiphosphines with in particular the systematic near-eclipsed conformation of aminomethyl groups. This conformation is at the origin of the unexpected formation at RT of a zwitterionic cyclopalladate from an (aminomethyl)ferrocene derivative, arising from intramolecular Cp-proton transfer to the proximate free amino group by simple C-H activation reaction in the presence of palladium dichloride.