N-(4-methylbenzylidene)-P,P-diphenylphosphinic amide | 154675-28-2

• 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: N-(4-methylbenzylidene)-P,P-diphenylphosphinic amide
• 英文别名: N-(4-methylbenzylidene)-P,P-diphenylphosphinamide；N-[(4-Methylphenyl)methylidene]-P,P-diphenylphosphinic amide；N-diphenylphosphoryl-1-(4-methylphenyl)methanimine
• CAS: 154675-28-2
• 化学式: C₂₀H₁₈NOP
• 分子量: 319.343
• InChiKey: TWDWLWZNOGJZTN-UHFFFAOYSA-N

物化性质

• 沸点：
  469.5±38.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  29.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(4-methylbenzylidene)-P,P-diphenylphosphinic amide 在 4-二甲氨基吡啶 、 strontium diisopropoxide 、 C₃₀H₂₈N₂O₄ 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， -60.0~20.0 ℃ 、101.33 kPa 条件下， 反应 16.0h， 生成 (3'S,5R)-3-benzoyl-1-(diphenylphosphoryl)-1'-methyl-2-thioxo-5-(p-tolyl)spiro[imidazolidine-4,3'-indolin]-2'-one
  参考文献：
  名称：

  异硫氰酸根合吲哚的曼尼希型反应催化不对称合成吡咯并吲哚

  摘要：

  易于获得：锶/席夫碱复合物作为标题反应的催化剂，可通过以下途径直接访问对映体富集的螺[咪唑烷-4,3'-羟吲哚]化合物以及螺[咪唑啉-4,3'-羟吲哚]由曼尼希加合物进行的两步转化。

  DOI：

  10.1002/anie.201203005
• 作为产物：
  描述：

  二苯基次膦酰氯 在 titanium(IV) tetraethanolate 、 氨 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 N-(4-methylbenzylidene)-P,P-diphenylphosphinic amide
  参考文献：
  名称：

  Nucleophilic addition of TMSCCl3 to N-phosphinoyl benzaldimines: a route to N-phosphinoyl-α-(trichloromethyl)benzylamines

  摘要：

  Nucleophilic addition of readily available TNISCCl3 to N-phosphinoyl benzaldimines allows preparation of N-phosphinoyl-alpha-(trichloromethyl)benzylamines. Typically, the reaction in THF at room temperature using tetrabutylammonium difluorotriphenylsilicate (TBAT) as a catalytic promoter, afforded very good yields (65-95% range) for most derivatives within 1 h at room temperature. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.08.122

文献信息

• The Supersilyl Group as a Carboxylic Acid Protecting Group: Application to Highly Stereoselective Aldol and Mannich Reactions
  作者：Jiajing Tan、Matsujiro Akakura、Hisashi Yamamoto

  DOI：10.1002/anie.201300102

  日期：2013.7.8

  Silyl superpowers: The supersilyl group was investigated as a superior carboxylic acid protecting group. Supersilyl esters were also utilized as stable carboxylic acid synthetic equivalents in highly stereoselective aldol and Mannich reactions (see scheme). The value of this method lies in easy photodeprotection and in the rapid synthesis of polyketide subunits.

  甲硅烷基超能力：超甲硅烷基被研究为一种优良的羧酸保护基团。超甲硅烷基酯也被用作高立体选择性羟醛和曼尼希反应中稳定的羧酸合成等价物（参见方案）。这种方法的价值在于容易的光去保护和聚酮亚基的快速合成。
• Direct Catalytic Asymmetric Mannich-Type Reactions of γ-Butenolides: Effectiveness of Brønsted Acid in Chiral Metal Catalysis
  作者：Akitake Yamaguchi、Shigeki Matsunaga、Masakatsu Shibasaki

  DOI：10.1021/ol800756r

  日期：2008.6.5

  Direct catalytic asymmetric Mannich-type reactions of gamma-butenolides are described. A chiral Lewis acid/amine base/Bronsted acid combination was used to catalyze a gamma-addition of gamma-butenolides to N-diphenylphosphinoyl imines, affording the products in up to >99% yield, anti/syn = >97:3, and 84% ee. The use of a catalytic amount of TfOH in addition to La(OTf)3/Me-PyBox/TMEDA was important

  描述了γ-丁烯内酯的直接催化不对称曼尼希型反应。手性路易斯酸/胺碱/布朗斯台德酸的组合用于催化γ-丁烯内酯向N-二苯基膦酰基亚胺的γ加成反应，从而使产物收率最高> 99％，反/ syn => 97：3，并且84％ee。除La（OTf）3 / Me-PyBox / TMEDA外，还使用催化量的TfOH对于提高收率和立体选择性很重要。
• Iron-Catalyzed Asymmetric Nitro-Mannich Reaction
  作者：Agata Dudek、Jacek Mlynarski

  DOI：10.1021/acs.joc.7b01786

  日期：2017.10.20

  The first enantioselective addition of nitroalkanes to imines (nitro-Mannich reaction), mediated by an iron(II) catalyst assembled by a hindered hydroxyethyl-pybox ligand, is described. This valuable carbon–carbon bond-forming reaction proceeds smoothly at room temperature to afford enantioenriched β-nitro amines in good yields and high enantioselectivity, up to 98% with unprecedentedly low iron catalyst

  描述了由受阻的羟乙基-Pybox配体组装的铁（II）催化剂介导的硝基链烷烃向亚胺的第一次对映选择性加成（硝基-曼尼希反应）。这种有价值的碳-碳键形成反应可在室温下顺利进行，以高收率和高对映选择性提供对映体富集的β-硝基胺，在前所未有的低铁催化剂负载量（5 mol％）下可达到98％。
• Highly Diastereo- and Enantioselective Cu-Catalyzed Borylative Coupling of 1,3-Dienes and Aldimines
  作者：Liyin Jiang、Peng Cao、Min Wang、Bin Chen、Bing Wang、Jian Liao

  DOI：10.1002/anie.201607493

  日期：2016.10.24

  A Cu‐catalyzed diastereo‐ and enantioselective borylative coupling reaction of 1,3‐dienes with imines was realized. Branched homoallylic amines are readily prepared in a syn‐selective manner with high regio‐, diastereo‐ and enantioselectivity. Moreover, these three‐component coupling reactions feature good functional‐group compatibility and easy access to the substrates and catalyst.

  实现了1,3-二烯与亚胺的Cu催化的非对映和对映选择性的硼基偶联反应。支链均烯胺很容易以顺选择性方式制备，具有很高的区域，非对映和对映选择性。此外，这些三组分偶联反应具有良好的官能团相容性，并且易于接近底物和催化剂。
• Asymmetric Addition of Terminal Alkynes to<i>N</i>-(Diphenylphosphinoyl)imines Promoted by Stoichiometric Amounts of a Proline-Derived β-Amino Alcohol
  作者：Wenjin Yan、Bin Mao、Shaoqun Zhu、Xianxing Jiang、Zhongli Liu、Rui Wang

  DOI：10.1002/ejoc.200900342

  日期：2009.8

  preparation of optically active propargylamines is described. The alkynylation of aromatic, heteroaromatic, aliphatic and α,β-unsaturated N-(diphenylphosphinoyl)imines was investigated by using diethylzinc and a proline-derived β-amino alcohol. N-(Diphenylphosphinoyl)-protected propargylic amines can be synthesized in high yields and with good to excellent enantioselectivities. (© Wiley-VCH Verlag GmbH

  描述了一种用于制备光学活性炔丙胺的新合成方法。通过使用二乙基锌和脯氨酸衍生的 β-氨基醇研究了芳香族、杂芳香族、脂肪族和 α,β-不饱和 N-（二苯基膦酰基）亚胺的炔基化反应。N-(二苯基膦酰基)-保护的炔丙胺可以以高产率合成，并且具有良好到优异的对映选择性。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)