1'-(dicyclohexylphosphino)-1-bromoferrocene | 952586-77-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: 1'-(dicyclohexylphosphino)-1-bromoferrocene
• 英文别名: 5-bromocyclopenta-1,3-diene;dicyclohexyl(cyclopenta-2,4-dien-1-yl)phosphane;iron(2+)
• CAS: 952586-77-5
• 化学式: C₂₂H₃₀BrFeP
• 分子量: 461.205
• InChiKey: HDVCFDXLSXEOBB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.34
• 重原子数：
  25
• 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：

  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
• 作为产物：
  描述：

  1,1'-dibromoferrocene 、 二环己基氯化膦 在 正丁基锂 作用下， 以Ca. 40 %的产率得到1'-(dicyclohexylphosphino)-1-bromoferrocene
  参考文献：
  名称：

  二茂铁膦斯替宾的合成、反应性和配位行为及其 P(V) 和 Sb(V) 衍生物的分子内相互作用

  摘要：

  与 P,N-类似物相比，结合 P 和 Sb 取代基的化合物仍然不太常见。该贡献描述了新的二茂铁膦斯蒂宾 Cy 2 PfcSbPh 2 ( 3 ; fc = 二茂铁-1,1′-二基，Cy = 环己基)的合成，及其在膦和锑化部分修饰的衍生物，即。, Cy 2 P(E)fcSbPh 2 (E = BH 3 , O, S, AuCl), Cy 2 P(E)fcSbCl 2 Ph 2 (E = BH 3 , S, AuCl) 和苯乙烯 Cy 2 P(E) fcSb(O 2 C 6 Cl 4 )Ph 2（E = 空、BH 3、O、S 和 AuCl）。儿茶酚锑硼烷 Cy 2 PfcSb(O 2 C 6 Cl 4 )Ph 2和 Cy 2 P(O)fcSb(O 2 C 6 Cl 4 )Ph 2中 Sb 原子的路易斯酸性增加导致分子内 P → Sb 和 O → Sb 配位相互作用，在各自的母体锑中或什至在 Cy

  DOI：

  10.1039/d4nj00349g

文献信息

• [EN] BIDENTATE CHIRAL LIGANDS FOR USE IN CATALYTIC ASYMMETRIC ADDITION REACTIONS<br/>[FR] LIGANDS CHIRAUX BIDENTATES UTILISABLES DANS DES RÉACTIONS D'ADDITION CATALYTIQUES ASYMÉTRIQUES
  申请人：SOLVIAS AG

  公开号：WO2009065784A1

  公开（公告）日：2009-05-28

  Compounds of the formula (I), in the form of mixtures comprising predominantly one diastereomer or in the form of pure diastereomers, Z1-Q-P*R0R1 (I) in which Z1 is a C-bonded, secondary phosphine group -P(R)2; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals, or Z1 is the -P*R0R1 group; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C1-C4-alkylene skeleton, and in which base skeletons a secondary phosphine group Z1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group, and in which base skeletons a P-chiral group -P*R0R1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; R0 is methyl or hydroxyl, and R0 is methyl when Z1 is the -P*R0R1 group; and R1 is a C-bonded optically enriched or optically pure chiral, mono- or polycyclic, nonaromatic hydrocarbon or heterohydrocarbon radical which has 3 to 12 ring atoms and 1 to 4 rings and which has a stereogenic carbon atom at least in the α position to the P-C bond; Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

  化合物的公式（I）的形式，以主要包含一种对映异构体的混合物形式或纯对映异构体的形式，Z1-Q-P*R0R1（I），其中Z1是C-键合的次磷酸基团-P（R）2；其中R分别是烃基或杂烃基，或Z1是-P*R0R1基团；Q是二价的、不对映的、芳香基骨架，二价的、不对映的二茂铁基骨架，一个可选择取代的二价环烷烃或杂环烷烃骨架，或一个C1-C4-烷基骨架，并且在这些基骨架中，次磷酸基团Z1直接键合到一个碳原子，或者在环状基骨架的情况下，直接键合到一个碳原子或通过一个C1-C4-烷基团，以及在这些基骨架中，一个P-手性基团-P*R0R1直接键合到一个碳原子，或者在环状基骨架的情况下，直接键合到一个碳原子或通过一个C1-C4-烷基团到一个碳原子，以使磷原子通过1到7个碳链原子连接，这些碳链原子可以通过来自O、S、N、Fe或Si的杂原子间断连接；P*是一个手性磷原子；R0是甲基或羟基，当Z1是-P*R0R1基团时，R0是甲基；R1是一个C-键合的光学富集或光学纯的手性、单环或多环、非芳香烃基或杂烃基，具有3到12个环原子和1到4个环，并且至少在P-C键的α位置具有一个立体异构碳原子；这些配体的金属络合物是用于不对称加成反应的均相催化剂，特别是氢化反应。
• ChenPhos: Highly Modular P-Stereogenic<i>C</i>₁-Symmetric Diphosphine Ligands for the Efficient Asymmetric Hydrogenation of α-Substituted Cinnamic Acids
  作者：Weiping Chen、Felix Spindler、Benoit Pugin、Ulrike Nettekoven

  DOI：10.1002/anie.201304472

  日期：2013.8.12

  cats are purrfectionists: The ChenPhos ligands (see structure) showed dramatically higher catalytic activity in the title reaction than their C2‐symmetric predecessor with two dimethylaminoethyl‐substituted ferrocenyl(phenyl)phosphanyl groups. The ready accessibility, extreme air stability, and high enantioselectivity, activity, and productivity of these ligands make them very promising for a wide range

  这些猫是纯粹主义者：ChenPhos配体（参见结构）在标题反应中比其带有两个二甲基氨基乙基取代的二茂铁基（苯基）膦酰基的C 2对称对称异构体显示出更高的催化活性。这些配体易于获得，极高的空气稳定性以及高对映选择性，活性和生产率，使它们在广泛的实际应用中非常有前途。
• Selective borane reduction of phosphinoferrocene carbaldehydes to phosphinoalcohol–borane adducts. The coordination behaviour of 1-(diphenylphosphino)- 1′-(methoxymethyl)ferrocene, a new ferrocene O,P-hybrid donor prepared from such an adduct
  作者：Petr Štěpnička、Ivana Císařová

  DOI：10.1039/c2dt32511j

  日期：——

  temperatures favoured the formation of methyl derivatives (e.g., Ph2PfcCH3·BH3 (8)) resulting from overreduction (deoxygenation). The crystal structures of 3, 5, (Sp)-7, 8 and Cy2PfcBr (9) have been determined by single-crystal X-ray diffraction analysis. The crystal assemblies of adducts 5 and (Sp)-7 are built up by means of C–H⋯O contacts, O–H⋯HB dihydrogen bonds and other soft interactions but, surprisingly

  该还原的二茂铁膦基醛，R 2 PfcCHO（R =苯基，2 ; CY，3 ; FC =二茂铁-1,1'-二基中，Cy =环己基）和（小号p） - [铁（η 5 -C 5 ħ 3 -1-CHO-2-PPH 2）（η 5 -C 5 H ^ 5）]（（小号p） - 4）中，用BH 3 ·THF或BH 3 ·SMe的2在0℃下在THF中选择性地得到相应的膦醇-硼烷加合物R 2 PfcCH 2 OH·BH 3（R = Ph，5; CY，6）和（小号p） - [铁（η 5 -C 5 H ^ 3 -1-CH 2 OH-2-PPH 2）（η 5 -C 5 H ^ 5）]·BH 3（（小号p） - 7），以定量产率。相反，在高温下进行的反应有利于由于过度还原（脱氧）而形成甲基衍生物（例如，Ph 2 PfcCH 3 ·BH 3（8））。的晶体结构3，5（小号p） - 7，8和Cy 2 PfcBr（9）已经通过
• Ferrocenediphosphines
  申请人：Chen Weiping

  公开号：US20090124812A1

  公开（公告）日：2009-05-14

  Compounds of the formula I in the form of enantiomerically pure diastereomers or a mixture of diastereomers, (I), where the radicals R 1 are identical or different and are each C 1 -C 4 -alkyl; m is 0 or an integer from 1 to 3; n is 0 or an integer from 1 to 4; R 2 is a hydrocarbon radical or a C-bonded heterohydrocarbon radical; Cp is unsubstituted or C 1 -C 4 -alkyl-substituted cyclopentadienyl; Y is a C-bonded chiral group which directs metals of metallation reagents into the ortho position; and Phos is a P-bonded P(III) substituent. The compounds are chiral ligands for complexes of transition metals which are used as homogeneous catalysts in asymmetric syntheses.

  化学式为I的化合物形式为对映纯的非对映异构体或非对映异构体的混合物，其中基团R1相同或不同，且均为C1-C4烷基；m为0或1至3的整数；n为0或1至4的整数；R2为碳氢基团或C键结合的杂环碳氢基团；Cp为未取代或C1-C4烷基取代的环戊二烯基；Y为C键结合的手性基团，可将金属化试剂导向邻位位置；Phos为P键结合的P（III）取代基。这些化合物是过渡金属配合物的手性配体，用作不对称合成中的均相催化剂。
• Ferrocene‐Based Phosphenium Ion with Intramolecular Phosphine Coordination
  作者：Tianqing Zhang、Vladimir Ya. Lee、Shogo Morisako、Shinobu Aoyagi、Takahiro Sasamori

  DOI：10.1002/ejic.202100615

  日期：2021.10.14

  ion with intramolecular phosphine-coordination, incorporated within [2]ferrocenophane framework, was synthesized as an air-stable compound. Although it can be thought as a phosphino-phosphonium derivative, considering the potential rotation of the cyclopentadienyl group of the ferrocene moiety, the isolated compound should be a masked phosphenium ion with intramolecular phosphine coordination. The redox

  具有分子内膦配位的双（二茂铁基）鏻离子结合在 [2] 二茂铁骨架中，合成为空气稳定化合物。虽然它可以被认为是一种膦衍生物，但考虑到二茂铁部分的环戊二烯基的潜在旋转，分离出的化合物应该是一个带有分子内膦配位的掩蔽鏻离子。通过 CV 测量和理论计算揭示了分离的膦配位鏻离子的氧化还原行为，表明其在二茂铁基部分的氧化和在磷中心的还原连续产生相应的膦自由基和磷离子。