1-di(2-(5-methylfuryl)phosphanyl)ferrocene | 525603-48-9

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: 1-di(2-(5-methylfuryl)phosphanyl)ferrocene
• 英文别名: 1-dicyclohexylphosphinoferrocene；(dicyclohexylphosphino)ferrocene；(dicyclohexylphosphinyl)ferrocene；FcPCy2；[iron(η5-C5H5)(η5-C5H4P(cyclohexyl)2)]；dicyclohexylferrocenyl-phospine；Cyclopenta-1,3-diene;dicyclohexyl(cyclopenta-1,3-dien-1-yl)phosphane;iron(2+)
• CAS: 525603-48-9
• 化学式: C₂₂H₃₁FeP
• 分子量: 382.309
• InChiKey: KFGVRWGDTLZAAO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.58
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  乙烯基二苯基膦 、 1-di(2-(5-methylfuryl)phosphanyl)ferrocene 在 iron(III) chloride 、 D-脯氨酸 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以93%的产率得到(R)-1-[(Sp)-2-(dicyclohexylphosphino)ferrocenylethyl]diphenylphosphine
  参考文献：
  名称：

  Josiphos类手性二茂铁膦配体的合成方法

  摘要：

  本发明公开了一种Josiphos 类手性二茂铁膦配体的合成方法，属于有机合成领域。该方法通过如下步骤实现：以二茂铁为起始原料，三氯化铝的催化剂，与膦氯化合物R2PCl反应，然后在三氯化铁和D‑脯氨酸的催化作用下与乙烯基二芳基膦反应得到Josiphos 类手性二茂铁膦配体。本发明与现有技术相比步骤少，操作简单，降低了生产成本，适合工业化生产。制得的Josiphos 类手性二茂铁膦配体可作为金属催化剂的配体，催化不对称有机反应，应用于医药合成等领域。

  公开号：

  CN105949248B
• 作为产物：
  描述：

  1'-(dicyclohexylphosphino)-1-bromoferrocene 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 1-di(2-(5-methylfuryl)phosphanyl)ferrocene
  参考文献：
  名称：

  Carbosilane-supported (p-cymene) ruthenium ferrocenyl phosphines in the β-oxopropyl ester synthesis

  摘要：

  The synthesis and characterization of a series of carbosilane-supported ferrocenyl phosphine ruthenium complexes of type siMe4,(Ee(eta(5)-CsH(4)SiMez(CF1213)(eta(5)-CsF14PR2)RuC12(116-P-cymene))),, (p-cymene = i-Pr-4-Me-C6H4; n = 2: 10a, R = Ph; 10b, R = cC(6)H(11); 10c, R = 2-(5-Me)C4H20); n = 4: 11a, R = Ph; 11b, R = (C6H11)-C-c; 11c, R = 2-(5-Me)C4H20)) is described. For comparative reasons, the non-immobilized ferrocenyl phosphine ruthenium complexes [FcPR(2)(RuCl2(126-p-cymene))I (Ec = Ee(eta(5)-05H(4))(eta(5)-05F(15)); 9a, R = Ph; 9b, R = (C6H11)-C-c; 9c, R = 2-(5-Me)C4H20) were prepared. The molecular structure of 9c in the solid state is reported confirming the expected tetrahedral coordination sphere about the phosphorus atom and the "piano-stool" geometry about ruthenium. The ruthenium complexes 9-11 are catalytically active in the addition of benzoic acid to propargyl alcohol to form d-oxopropyl benzoate. The obtained activities and productivities show that a good solubility of the catalyst is necessary for a successful catalytic reaction. Furthermore, the rate of the reaction can be influenced by using less basic and electronwithdrawing phosphine ligands. (C) 2015 Elsevier BY. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2015.02.036
• 作为试剂：
  描述：

  2,2-dibromo-1-(3,4-dimethoxyphenyl)ethene 在 哌啶 、 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 1-di(2-(5-methylfuryl)phosphanyl)ferrocene 、 正丁基锂 、 [RhCl(coe)2]2 、 4 A molecular sieve 、 sodium methylate 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 三甲基氢氧化锡 作用下， 以 甲醇 、 正己烷 、 氯仿 、 1,2-二氯乙烷 、 甲苯 、 苯 为溶剂， 反应 124.83h， 生成 4-{2-[1-carboxy-2-(3,4-dimethoxyphenyl)ethoxycarbonyl]vinyl}-2-(3,4-dimethoxyphenyl)-7-methoxy-2,3-dihydrobenzofuran-3-carboxylic acid
  参考文献：
  名称：

  Total Synthesis of (+)-Lithospermic Acid by Asymmetric Intramolecular Alkylation via Catalytic C−H Bond Activation

  摘要：

  The total synthesis of (+)-lithospermic acid is described. The efficient synthesis features an asymmetric alkylation via C-H bond activation to assemble the dihydrobenzofuran core of the natural product. This was accomplished via a chiral imine-directed C-H bond functionalization and represents the first application of this C-H activation method to natural product synthesis. Furthermore, a challenging deprotection of a late-stage permethylated lithospermic acid was achieved.

  DOI：

  10.1021/ja052680h

文献信息

• (Metallocenylphosphane)palladium Dichlorides – Synthesis, Electrochemistry and Their Application in C–C Coupling Reactions
  作者：Bianca Milde、Manja Lohan、Claus Schreiner、Tobias Rüffer、Heinrich Lang

  DOI：10.1002/ejic.201100842

  日期：2011.12

  appropriate Pd complexes are oxidized at more positive potentials. Depending on the phosphane or selenophosphane, follow-up reactions occur, which are discussed. In contrast, the palladium complexes show reversible redox behavior. UV/Vis/NIR spectroelectrochemical studies carried out on 9b indicate an electrostatic interaction between the two terminal ferrocenyl groups. All of the palladium complexes were

  PR2Mc/Se=PR2Mc [Mc = Fc = Fe(η5-C5H4)(η5-C5H5), R = C6H5 (3a/4a), 2-MeC6H4 (3b/4b) 的一系列茂金属膦的合成和表征)、c-C4H3O (3c/4c)、tBu (3d/4d)、c-C6H11 (3e/4e)；Mc = Rc = Ru(η5- )(η5- ), R = (6a/7a), 2-MeC6H4 (6b/7b), c- (6c/7c), c- (6d/7d) )] 及其钯配合物 [PdCl2(PR2Mc)2] [Mc = Fc, R = (9a), 2-MeC6H4 (9b), c- (9c), tBu (9d), c- (9e) ; 报道了 Mc = Rc、R = (10a)、2-MeC6H4 (10b)、c- (10c)、c-
• Synthesis and catalytic properties of palladium(ii) complexes with P,π-chelating ferrocene phosphinoallyl ligands and their non-tethered analogues
  作者：Karel Škoch、Jakub Antala、Ivana Císařová、Petr Štěpnička

  DOI：10.1039/d4dt00961d

  日期：——

  Hybrid phosphines usually combine a phosphine moiety with another heteroatom secondary donor group in their structures while compounds equipped with hydrocarbyl π–donor moieties remain uncommon. This contribution reports the synthesis and structural characterization of the first P/π-allyl-chelating complexes that were obtained using the structurally flexible and redox-active ferrocene unit as the scaffold

  杂化膦通常在其结构中将膦部分与另一个杂原子二级供体基团结合，而配备烃基π供体部分的化合物仍然不常见。该贡献报告了第一个 P/π-烯丙基螯合配合物的合成和结构表征，该配合物是使用结构灵活且具有氧化还原活性的二茂铁单元作为支架获得的，即。 [PdCl(R 2 PfcCHCHCH 2 -η 3 :κ P )] ( 1 R ；R = Ph 和环己基 (Cy)；fc = 二茂铁-1,1′-二基)。这些化合物是由各自的膦基二茂铁甲醛R 2 PfcCHO 与乙烯基溴化镁反应合成的，生成1-(膦基二茂铁基)烯丙醇，随后将其乙酰化。所得乙酸烯丙酯与[Pd 2 (dba) 3 ]/[Et 3 NH]Cl（dba=二亚苄基丙酮）顺利反应生成目标化合物。 配合物1 R及其非束缚类似物 [PdCl(η 3 -C 3 H 5 )(FcPR 2 -κ P )] ( 5 R ; Fc = 二茂铁基) 作为 Pd 催化乙酸
• Synthesis of Dihydropyridines and Pyridines from Imines and Alkynes via C−H Activation
  作者：Denise A. Colby、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/ja7104784

  日期：2008.3.1

  A convenient one-pot C-H alkenylation/electrocyclization/aromatization sequence has been developed for the synthesis of highly substituted pyridine derivatives from alkynes and alpha,beta-unsaturated N-benzyl aldimines and ketimines that proceeds through dihydropyridine intermediates. A new class of ligands for C-H activation was developed, providing broader scope for the alkenylation step than could be achieved with previously reported ligands. Substantial information was obtained about the mechanism of the reaction. This included the isolation of a C-H activated complex and its structure determination by X-ray analysis; in addition, kinetic simulations using the Copasi software were employed to determine rate constants for this transformation, implicating facile C-H oxidative addition and slow reductive elimination steps.