diphenylphosphino-phenyl-ferrocenyl-ethylbis[3,5-bis-(trifluoromethyl)phenyl]phosphine | 945020-19-9

• 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: diphenylphosphino-phenyl-ferrocenyl-ethylbis[3,5-bis-(trifluoromethyl)phenyl]phosphine
• 英文别名: 1-{2-[2-(diphenylphosphino)phenyl]ferrocenyl}ethylbis[3,5-bis(trifluoromethyl)phenyl]phosphine；walphos；(S)-1-{(Sp)-2-[2-(diphenylphosphino)phenyl]ferrocenyl}ethylbis[3,5-bis-(trifluoromethyl)phenyl]phosphine；(R)-(-)-1-[(R)-2-(2′-diphenylphosphinophenyl)ferrocenyl]ethylbis(di-3,5-trifluoromethylphenyl)phosphine；(R,R)-Walphos W-0001-1；bis[3,5-bis(trifluoromethyl)phenyl]-[(1R)-1-[2-(2-diphenylphosphanylphenyl)cyclopenta-2,4-dien-1-yl]ethyl]phosphane;cyclopenta-1,3-diene;iron(2+)
• CAS: 945020-19-9
• 化学式: C₄₆H₃₂F₁₂FeP₂
• 分子量: 930.535
• InChiKey: FEDNCBFOAIDORO-KHZPMNTOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.5
• 重原子数：
  61
• 可旋转键数：
  8
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  [(μ-H)₄Ru₄(CO)₁₂] 、 diphenylphosphino-phenyl-ferrocenyl-ethylbis[3,5-bis-(trifluoromethyl)phenyl]phosphine 在 氢气 作用下， 以 苯 为溶剂， 100.0 ℃ 、2.5 MPa 条件下， 反应 4.0h， 以73%的产率得到
  参考文献：
  名称：

  高效的基于簇的催化剂，用于α-不饱和羧酸的不对称加氢

  摘要：

  新簇[H 4 Ru 4（CO）10（μ-1,2-P-P）]，[H 4 Ru 4（CO）10（1,1-P-P）]和[H 4 Ru 4（CO）11（P-P）]（P-P =基于二茂铁的Josiphos或Walphos配体家族的手性二膦）已被合成并表征。11个簇的晶体和分子结构揭示了[H 4 Ru 4（CO）10（μ1,2-P-P）]簇对于Josiphos和Walphos配体是不同的。Josiphos配体以“常规”方式桥接钌四面体的金属-金属键，即两个膦部分相对于四面体的三角形面在赤道位置配位，而Walphos配体的膦部分在一轴向和一赤道位置。两种类型的配体之间的配体尺寸和配位模式的差异似乎反映在异构化的相对倾向上。在溶液中，[H 4 Ru 4（CO）10（1,1-Walphos）]团簇异构化为相应的[H 4 Ru 4（CO）10（μ1,2-Walphos）]团簇，而含Josiphos的团簇在溶液

  DOI：

  10.1002/chem.201200630
• 作为试剂：
  描述：

  甲醇 、 苯甲醛 、 苯基乙烯基砜 、 2-amino-1-(1,1-dioxidobenzo[d]isothiazol-2(3H)-yl)ethanone 在 tetrakis(actonitrile)copper(I) hexafluorophosphate 、 diphenylphosphino-phenyl-ferrocenyl-ethylbis[3,5-bis-(trifluoromethyl)phenyl]phosphine 、 dipotassium hydrogenphosphate 作用下， 以 甲苯 为溶剂， 反应 5.0h， 以60%的产率得到(2S,4R,5S)-methyl 5-phenyl-4-(phenylsulfonyl)pyrrolidine-2-carboxylate
  参考文献：
  名称：

  Catalytic Asymmetric Exo-Selective [C+NC+CC] Reaction

  摘要：

  A catalytic asymmetric version of the exoselective [C+NC+CC] reaction is reported. This multicomponent reaction utilizes a readily prepared achiral glycyl sultam as the "NC" component and commercially available catalyst components. The method can be applied to a variety of aldehydes ("C" component) and activated alkenes ("CC" component) to provide substituted pyrrolidines in good yields and high enantioselectivities. Of particular note is the ability to employ labile enolizable aldehydes (e.g., acetaldehyde and propionaldehyde) in this reaction.

  DOI：

  10.1021/ol500474a

文献信息

• Diastereomeric control of enantioselectivity: evidence for metal cluster catalysis
  作者：Ahmed F. Abdel-Magied、Amrendra K. Singh、Matti Haukka、Michael G. Richmond、Ebbe Nordlander

  DOI：10.1039/c4cc02319f

  日期：——

  Enantioselective hydrogenation of tiglic acid effected by diastereomers of the general formula [(μ-H)₂Ru₃(μ₃-S)(CO)₇(μ-P–P*)] (P–P* = chiral Walphos diphosphine ligand) strongly supports catalysis by intact Ru₃ clusters.

  川芎酸的对映选择性加氢受到一般公式[(μ-H)₂Ru₃(μ₃-S)(CO)₇(μ-P–P*)]（P–P* = 手性Walpohs二膦配体）的二对映体的影响，强有力地支持Ru₃团簇的催化作用。
• Asymmetric hydrogenation of an α-unsaturated carboxylic acid catalyzed by intact chiral transition metal carbonyl clusters – diastereomeric control of enantioselectivity
  作者：Ahmed F. Abdel-Magied、Yusuf Theibich、Amrendra K. Singh、Ahibur Rahaman、Isa Doverbratt、Arun K. Raha、Matti Haukka、Michael G. Richmond、Ebbe Nordlander

  DOI：10.1039/c9dt04799a

  日期：——

  Asymmetric hydrogenation catalysis by [(μ-H)₂Ru₃(μ₃-S)(CO)₇(μ-P–P*)] (P–P* = chiral diphosphine) indicates intact chiral clusters as active catalysts.

  [(μ-H)₂Ru₃(μ₃-S)(CO)₇(μ-P–P*)]（P–P* = 手性二膦）通过不对称氢化催化表明完整的手性团簇作为活性催化剂。
• Chiral diphosphine derivatives of alkylidyne tricobalt carbonyl clusters – A comparative study of different cobalt carbonyl (pre)catalysts for (asymmetric) intermolecular Pauson–Khand reactions
  作者：M. Abdul Mottalib、Matti Haukka、Ebbe Nordlander

  DOI：10.1016/j.poly.2015.04.021

  日期：2016.1

  Reaction of the tricobalt carbyne cluster [Co3(μ3-CH)(CO)9] with chiral diphosphines of the Josiphos and Walphos families affords the new clusters [Co3(μ3-CH)(CO)7(P–P∗)] in good yield (P–P∗ = J004 (1), J005 (2), J007 (3), W001 (4), W003 (5)). The new alkylidyne tricobalt clusters, and the previously known [Co3(μ3-CH)(CO)7(μ-J003)], have been tested as catalysts/catalyst precursors for intermolecular

  所述三钴碳炔簇的反应[CO 3（μ 3 -CH）（CO）9 ]与Josiphos和Walphos家庭手性二膦，得到新的簇[CO 3（μ 3 -CH）（CO）7（P-P **）]的产量高（P–P **  = J004（1），J005（2），J007（3），W001（4），W003（5））。新的次烷基三钴簇，先前已知的[CO 3（μ 3 -CH）（CO）7（μ-J003）]，已被测试为使用降冰片烯和苯基乙炔作为分子间Pauson-Khand环化反应的催化剂/催化剂前体。事实证明，二膦取代的三叶羰基羰基簇是可行的催化剂/催化剂前体，其产生的产物具有中等至良好的收率，但对映体过量较低。当使用[Co 2（CO）8 ]或[Co 4（CO）12 ]作为催化剂前体，手性二膦配体用作同一Pauson-Khand反应的促进剂/辅助配体时，总收率和选择性都很高关于环戊烯酮的形成有显着改善。配位体J007和W001与[Co
• Synthesis, Coordination Behavior, and Use in Asymmetric Hydrogenations of Walphos-Type Ligands
  作者：Yaping Wang、Thomas Sturm、Marianne Steurer、Vladimir B. Arion、Kurt Mereiter、Felix Spindler、Walter Weissensteiner

  DOI：10.1021/om701103d

  日期：2008.3.24

  A total of nine Walphos-type diphosphine ligands, all of which have a ferrocenyl-aryl backbone, have been synthesized, characterized, and tested in asymmetric ruthenium-, rhodium-, and iridium-catalyzed hydrogenations of alkenes, ketones, and one imine. Ruthenium- and rhodium-mediated hydrogenations of alkenes and ketones gave enantioselectivities of up to 95% and 97% ee, respectively. Ligand tuning was attempted by variation of the phosphorus-bound aryl and alkyl substituents and by attaching electron-donating or electron-withdrawing substituents to the backbone phenyl ring. Dichloropalladium(II) complexes of five ligands were synthesized, and in four cases the molecular structures were studied in solution as well as in the solid state.
• Taniaphos and Walphos ligands: Oxidative electrochemistry and complexation. Synthesis, characterization, oxidative electrochemistry and X-ray structures of [(Taniaphos/Walphos)MCl2] (M=Pd or Pt)
  作者：Annalese F. Maddox、Arnold L. Rheingold、James A. Golen、W. Scott Kassel、Chip Nataro

  DOI：10.1016/j.ica.2007.09.031

  日期：2008.7

  The oxidative electrochemistry of chiral, bidentate ferrocenylphosphines five Taniaphos and seven Walphos ligands, was studied in methylene chloride. In general, two waves of varying reversibility were observed. Complexes of the general type [(phosphine) MCl2] (phosphine = Taniaphos or Walphos; M = Pd or Pt) were prepared and characterized by NMR. Upon coordination, the oxidative electrochemistry of the ligands was greatly simplified. The X-ray structures of a Taniaphos platinum complex as well as a palladium and a platinum complex with a Walphos ligand were determined. (C) 2007 Elsevier B.V. All rights reserved.