双(3,5二甲基4-甲氧苯基)磷 | 122708-97-8

• 物质功能分类: 有机原料 - 有机膦化合物
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 中文名称: 双(3,5二甲基4-甲氧苯基)磷
• 英文名称: bis(4-methoxy-3,5-dimethylphenyl)phosphine
• 英文别名: Bis(3,5-dimethyl-4-methoxyphenyl)phosphine；bis(4-methoxy-3,5-dimethylphenyl)phosphane
• CAS: 122708-97-8
• 化学式: C₁₈H₂₃O₂P
• 分子量: 302.353
• InChiKey: VNKFDSUAELUAQZ-UHFFFAOYSA-N

物化性质

• 沸点：
  416.6±45.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  双(3,5二甲基4-甲氧苯基)磷 、 (-)-1,4-二-O-甲苯磺酰基-2,3-O-异亚丙基-L-苏糖醇 在 正丁基锂 作用下， 生成 (4R-trans)-<(2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene)>bis
  参考文献：
  名称：

  Asymmetric Reactions Catalyzed by Chiral Metal Complexes. LVII. Synthesis of Efficient Chiral Bisphosphine Ligands, Modified DIOPs, (4R,5R)-4-(Diaryl- or dialkylphosphino)methyl-5-(diarylphosphino)methyl-2,2-dimethyl-1,3-dioxolanes, and Their Use in Rhodium(I)-Catalyzed Asymmetric Hydrogenations.

  摘要：

  改良的DIOPs，(4R, 5R)-4-(二芳基或二烷基磷酰基)甲基-5-(二芳基磷酰基)甲基-2, 2-二甲基-1, 3-二噁烷，基于我们的设计概念制备，并用作铑(I)催化的酮平滑酸、丁烯二酸、去甲基丁烯二酸酯和β-芳基取代丁烯二酸衍生物的不对称氢化的配体。含有二环己基磷酰基和二苯基磷酰基的(4R-trans)-二环己基[[5-[(二苯基磷酰基)甲基]-2, 2-二甲基-1, 3-二噁烷-4-基]甲基]磷酸盐（DIOCP）被发现是比原始DIOP在酮平滑酸的不对称氢化反应中更有效的催化剂。具有电子给体基团的改良DIOPs在其对位上是铑(I)催化的丁烯二酸及其衍生物不对称氢化的有效配体；特别是，(4R-trans)-[(2, 2-二甲基-1, 3-二噁烷-4, 5-双基)双(亚甲基)]双[双(4'-甲氧基-3', 5'-二甲基苯)磷]（MOD-DIOP）同时具有p-甲氧基基团和每个苯基上的两个m, m'-甲基基团，其对映选择性和催化活性显著高于DIOP。

  DOI：

  10.1248/cpb.41.1149
• 作为产物：
  描述：

  di(3,5-dimethyl-4-methoxyphenyl)phosphine oxide 在 三氯硅烷 、 三乙胺 作用下， 以 xylene 为溶剂， 生成 双(3,5二甲基4-甲氧苯基)磷
  参考文献：
  名称：

  Electronic and steric effects of ligands as control elements for rhodium-catalyzed asymmetric hydrogenation

  摘要：

  Chiral diphosphine ligands analogous to bdpp have been synthesized and tested in order to study the effect of the electronic nature of the ligands in Rh-catalyzed asymmetric hydrogenation of some prochiral olefins. The results are compared with those obtained with the analogous unsubstituted ligand (bdpp). The rhodium-catalyzed asymmetric hydrogenation of olefins was influenced by ligand-based electronic effects, as well as substrate based ones. Excellent ee's (up to 98.3%) have been obtained in the rhodium-catalyzed hydrogenation of (Z)-alpha-acetamidocinnamic acids and esters. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.04.023

文献信息

• Construction of Benzo-1,2,3-thiazaphosphole Heterocycles by Annulations of <i>ortho</i>-Phosphinoarenesulfonyl Fluorides with Trimethylsilyl Azide
  作者：Wenjun Luo、Zhenguo Wang、Xiaohui Cao、Dacheng Liang、Mingjie Wei、Keshu Yin、Le Li

  DOI：10.1021/acs.joc.0c01309

  日期：2020.11.20

  Annulations of ortho-phosphinoarenesulfonyl fluorides with trimethylsilyl azide were developed to access an unprecedented benzo-1,2,3-thiazaphosphole heterocycle. A corresponding reaction mechanism was proposed and further elucidated by experimental and computational studies. The reaction proceeds through a Staudinger-type iminophosphorane intermediate followed by intramolecular trapping with sulfonyl

  开发了邻-膦基芳烃磺酰氟与三甲基甲硅烷基叠氮化物的环，以得到前所未有的苯并1,2,3-噻唑磷杂环。提出了相应的反应机理，并通过实验和计算研究进一步阐明。该反应通过Staudinger型亚氨基膦烷中间体进行，然后用磺酰氟进行分子内捕集。
• Efficient asymmetric syntheses of naturally occurring lignan lactones using catalytic asymmetric hydrogenation as a key reaction
  作者：Toshiaki Morimoto、Mitsuo Chiba、Kazuo Achiwa

  DOI：10.1016/s0040-4020(01)80536-6

  日期：1993.2

  using the catalytic asymmetric hydrogenation of arylidenesuccinic acid monoesters with a rhodium(I) complex of a chiral bisphosphine, (4S,5S)-MOD-DIOP. Asymmetric total syntheses of some naturally occurring lignans, (+)-collinusin, (−)-deoxypodophyllotoxin, and (+)-neoisostegane, were achieved via several steps from (R)-γ-butyrolactones as key intermediates obtained by the reduction of (R)-arylmethylsuccinic

  通过使用具有手性双膦（4 S，5 S）-MOD-DIOP的铑（I）配合物的芳基琥珀酸单酯催化不对称加氢反应，可以高效地获得光学纯的（R）-芳基甲基琥珀酸单甲酯。一些天然存在的木酚素的不对称全合成，（+） - collinusin，（ - ） -脱氧，和（+） - neoisostegane，分别实现通过几个步骤从（- [R）-γ丁内酯，如通过还原得到关键中间体（R）-芳基甲基琥珀酸单甲酯。
• Nickel-Catalyzed Asymmetric Reductive Cross-Coupling between Heteroaryl Iodides and α-Chloronitriles
  作者：Nathaniel T. Kadunce、Sarah E. Reisman

  DOI：10.1021/jacs.5b06466

  日期：2015.8.26

  A Ni-catalyzed asymmetric reductive cross-coupling of heteroaryl iodides and α-chloronitriles has been developed. This method furnishes enantioenriched α,α-disubstituted nitriles from simple organohalide building blocks. The reaction tolerates a variety of heterocyclic coupling partners, including pyridines, pyrimidines, quinolines, thiophenes, and piperidines. The reaction proceeds under mild conditions

  已开发出 Ni 催化的杂芳基碘化物和 α-氯腈的不对称还原交叉偶联。该方法从简单的有机卤化物构建块中提供对映体富集的 α,α-二取代腈。该反应耐受多种杂环偶联物，包括吡啶、嘧啶、喹啉、噻吩和哌啶。该反应在温和的室温条件下进行，不需要预生成有机金属亲核试剂。
• [EN] LIGANDS<br/>[FR] LIGANDS
  申请人：JOHNSON MATTHEY PLC

  公开号：WO2004111065A1

  公开（公告）日：2004-12-23

  A substituted paracyclophane is described of formula (I) wherein Xl and X2 are linking groups comprising between 2 to 4 carbon atoms, Y1 and Y2 are selected from the group consisting of hydrogen, halide, oxygen, nitrogen, alkyl, cycloalkyl , aryl or heteroaryl, Z1, Z2 and Z3 are substituting groups that optionally contain functional groups, a, b, c, d, e and f are 0 or l and a + b + c + d + e + f = 1 to 6. PreferablyX1 and X2 are -(C2H4)- and a + b + c + d + e + f = 1 or 2. The substituted paracyclophane provides transition metal catalysts that demonstrate high activity and selectivity for asymmetric reactions.

  描述了一种具有以下式（I）的取代对环戊烷，其中X1和X2是包含2到4个碳原子的连接基团，Y1和Y2选自氢、卤素、氧、氮、烷基、环烷基、芳基或杂环芳基，Z1、Z2和Z3是可选地含有官能团的取代基团，a、b、c、d、e和f为0或1，且a + b + c + d + e + f = 1到6。最好X1和X2为-(C2H4)-，且a + b + c + d + e + f = 1或2。这种取代对环戊烷提供了过渡金属催化剂，表现出对不对称反应具有高活性和选择性。
• Synthesis of (.BETA.-N-Sulfonylaminoalkyl)phosphines and Their Use in Palladium-Mediated Asymmetric Synthesis.
  作者：Shunji SAKURABA、Toshimi OKADA、Toshiaki MORIMOTO、Kazuo ACHIWA

  DOI：10.1248/cpb.43.927

  日期：——

  A series of (β-N-sulfonylaminoalkyl)phosphine ligands has been developed and employed for asymmetric palladium-catalyzed hydrosilylation and Heck-type hydroarylation, affording up to 72% ee and 90% yield.

  开发了一系列（β-N-磺酰氨基烷基）膦配体，并用于不对称钯催化的氢硅化和Heck类型的氢芳基化，获得了高达72%的光学纯度和90%的产率。