4-diphenylphosphanyl-butan-1-ol | 7526-70-7

• 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: 4-diphenylphosphanyl-butan-1-ol
• 英文别名: 4-(Diphenylphosphanyl)butan-1-OL；4-diphenylphosphanylbutan-1-ol
• CAS: 7526-70-7
• 化学式: C₁₆H₁₉OP
• 分子量: 258.3
• InChiKey: CUWXSUUZRCXWHQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-diphenylphosphanyl-butan-1-ol 在 四氟硼酸-二乙醚络合物 、 正丁基锂 、 硼烷 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (4-(bis(4-methoxyphenyl)phosphaneyl)butyl)diphenylphosphane
  参考文献：
  名称：

  Synthesis of achiral, but unsymmetric, seven-membered rhodium(I)-chelates for hydrogenation in the chiral environment of alkyl polyglucoside micelles

  摘要：

  Chiral rhodium(I) chelates containing a seven-membered ring are well-known active catalysts for the asymmetric hydrogenation of amino acid precursors. A high conformational flexibility allows their enantioselectivity to be strongly influenced by modifiers. Now we show the nature of the counter-ions to have a large influence in apolar solvents. In addition, the presence of micelle forming alkyl polyglycosides as amphiphiles causes a remarkable increase in the enantiomeric excess (%ee). However, on achiral catalysts this enantioselectivity inducing effect scarcely exceeds the standard deviation for the gas chromatographic determination of the enantiomeric ratio. This is also true for the application of unsymmetric P,P'-ligands such as 3-phosphinopropyl-phosphinites or butane-1,4-diyl-bis(phosphines) carrying different P'-aryl groups, for which synthetic routes are given. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(00)00845-7
• 作为产物：
  描述：

  4-溴-1-丁醇 、 三苯基膦 在 lithium 作用下， 以 四氢呋喃 为溶剂， 以60%的产率得到4-diphenylphosphanyl-butan-1-ol
  参考文献：
  名称：

  单保护二醇的非常简单的方法

  摘要：

  已显示来自猪胰腺的脂肪酶（PPL）选择性催化将1，n-二醇双乙酸烷酯水解为相应的单乙酸酯。

  DOI：

  10.1016/0040-4039(95)02273-2

文献信息

• Phosphine–phosphite ligands: chelate ring size vs. activity and enantioselectivity relationships in asymmetric hydrogenation
  作者：Gergely Farkas、Szabolcs Balogh、József Madarász、Áron Szöllősy、Ferenc Darvas、László Ürge、Maryse Gouygou、József Bakos

  DOI：10.1039/c2dt30386h

  日期：——

  A series of new phosphine–phosphite ligands P(C)nOP (n = 1–4) have been synthesized and used for rhodium-catalyzed asymmetric hydrogenation of prochiral olefins in order to study the effect of the chelate ring size. Excellent ees (up to 97.5%) were obtained in the hydrogenation of dimethyl itaconate and an increase of activity and enantioselectivity was observed in the hydrogenation of (Z)-α-acetamidocinnamic acid methyl ester with the increasing length of the backbone of the ligands.

  合成了一系列新型膦-亚磷酸酯配体P(C)nOP (n = 1-4)，并用于铑催化前手性烯烃的不对称氢化，以研究螯合环尺寸的影响。在衣康酸二甲酯的氢化中获得了优异的ee（高达97.5％），并且在（Z）-α-乙酰氨基肉桂酸甲酯的氢化中观察到随着配体主链长度的增加，活性和对映选择性增加。
• Chelation control in the hydroformylation of terminal alkenes
  作者：W. Roy Jackson、Patrick Parlmutter、Guem-Hee Suh

  DOI：10.1039/c39870000724

  日期：——

  Hydroformylation of phosphine-bearing terminal alkenes can lead to a complete reversal of regioselection to that observed for simpler alkenes.

  含膦的末端烯烃的加氢甲酰化可导致区域选择的完全逆转，这与较简单的烯烃所观察到的完全相同。
• ProPhos: A Ligand for Promoting Nickel-Catalyzed Suzuki-Miyaura Coupling Inspired by Mechanistic Insights into Transmetalation
  作者：Jin Yang、Michelle C. Neary、Tianning Diao

  DOI：10.1021/jacs.4c00370

  日期：2024.3.6

  “Ni-oxo” transmetalation pathway, applying PPh2Me as the ligand, and identify the formation of a nickel-oxo intermediate as the turnover-limiting step. Building on this insight, we develop a scaffolding ligand, ProPhos, featuring a pendant hydroxyl group connected to the phosphine via a linker. The design preorganizes both the nucleophile and the nickel catalyst, thereby facilitating transmetalation. This

  镍催化的铃木-宫浦偶联（Ni-SMC）具有降低制药工艺合成成本的潜力。然而，其应用受到反应速率慢、催化剂负载量高和杂环范围有限等挑战的限制。尽管最近进行了研究，但 Ni-SMC 中的金属转移机制（通常被视为限制营业额的步骤）仍然没有得到充分的了解。我们阐明了“Ni-oxo”金属转移途径，应用 PPh 2 Me 作为配体，并将镍-氧中间体的形成确定为周转限制步骤。基于这一见解，我们开发了一种支架配体 ProPhos，其特点是通过连接体与膦连接的羟基侧基。该设计预组织了亲核试剂和镍催化剂，从而促进金属转移。该催化剂在多种杂芳烃中表现出快速的动力学和强大的活性，催化剂负载量为 0.5–3 mol%。对于芳烃基材，催化剂负载量可以进一步降低至0.1 mol%。
• Immobilization of Carbonylnickel Complexes:  A Solid-State NMR Study
  作者：K. D. Behringer、J. Blümel

  DOI：10.1021/ic950756c

  日期：1996.1.1

  Silica is commonly modified with bifunctional phosphines like PPh(2)CH(2)CH(2)Si(OEt)(3) prior to immobilization of catalysts. Here, besides PPh(2)(CH2)(3)Si(OEt)(3), ligands that are more stable toward oxidation, namely PPh(2)(C6H4)Si(OEt)(3), PPh(2)(C6H4)SiMe(2)(OEt), and PPh(2)(CH2)(4)OH, are applied. The di- and tricarbonylnickel complexes of these ligands are synthesized, characterized by Ni-61, (31)p, C-13, and H-1 NMR and IR spectroscopy, and immobilized on silica. Alternatively, the corresponding phosphine-modified silicas are treated with Ni(CO)(4). The obtained materials are investigated by P-31 and C-13 solid-state NMR spectroscopy. Di- and tricarbonylnickel species can be distinguished by their different chemical shift anisotropies and also by their IR data. While the first route allows immobilization of both di- and tricarbonylnickel complexes, reaction of surface-bound phosphines with Ni(CO)(4) gives the tricarbonyl species exclusively. Among the different ligands, PPh(2)(CH2)(4)OH has optimal qualities: It gives high surface coverages without oxidation or cross-linking, and therefore narrow NMR lines, and it allows C-13 CP/MAS NMR spectroscopy.
• Rapid method of preparation of phospholanium perchlorates via intramolecular cyclizations of 4-hydroxybutylorganophosphines
  作者：W. Ronald Purdum、K. Darrell Berlin

  DOI：10.1021/jo00907a021

  日期：1975.9