N-(3-methylbenzylidene)-P,P-diphenylphosphinic amide | 374776-81-5

• 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-(3-methylbenzylidene)-P,P-diphenylphosphinic amide
• 英文别名: N-[(3-Methylphenyl)methylidene]-P,P-diphenylphosphinic amide；N-diphenylphosphoryl-1-(3-methylphenyl)methanimine
• CAS: 374776-81-5
• 化学式: C₂₀H₁₈NOP
• 分子量: 319.343
• InChiKey: XDQKRZVQRXARDU-UHFFFAOYSA-N

物化性质

• 沸点：
  478.2±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：

  (三氯甲基)三甲基硅烷 、 N-(3-methylbenzylidene)-P,P-diphenylphosphinic amide 在 四丁基二氟三苯硅酸铵 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以72%的产率得到P,P-diphenyl-N-(2,2,2-trichloro-1-(m-tolyl)ethyl)phosphinic 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
• 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-(3-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。
• 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。
• Carbamoyl anion-initiated cascade reaction for stereoselective synthesis of substituted α-hydroxy-β-amino amides
  作者：Chao-Yang Lin、Peng-Ju Ma、Zhao Sun、Chong-Dao Lu、Yan-Jun Xu

  DOI：10.1039/c5cc08118a

  日期：——

  A carbamoyl anion-initiated cascade reaction with acylsilanes and imines allows rapid construction of substituted [small alpha]-hydroxy-[small beta]-amino amides in high yields with excellent diastereoselectivities.

  与酰基硅烷和亚胺的氨基甲酰基阴离子引发的级联反应可以高产量快速构建取代的[α]-羟基-[β]-氨基酰胺，同时具有出色的非对映选择性。
• Enantioselective Addition of Dialkylzinc to Aromatic Aldimines Mediated by Camphor-Derived Chiral β-Amino Alcohols
  作者：Wei-Ming Huang、Biing-Jiun Uang

  DOI：10.1002/asia.201403240

  日期：2015.4

  The enantioselective addition of diethylzinc or dimethylzinc to N‐(diphenylphosphinoyl)imines mediated by 1 or 2 could be achieved in high yields (70–97 %) and enantioselectivities (85–98 % ee). The catalytic loading of 1 or 2 a could be reduced to 10 mol % for methylation or ethylation of imines in high yields and enantioselectivities (79–96 %) when the reaction was conducted in the presence of 1

  在1或2介导的N-（二苯基膦酰基）亚胺中对二乙基锌或二甲基锌的对映选择性加成（70-97％）和对映选择性（85-98％ee）可以实现。当反应在1.8当量甲醇的存在下进行时，亚胺的甲基化或乙基化反应可以将1或2 a的催化负载降低至10 mol％，从而获得高收率和对映选择性（79-96％）。ñ单取代的氨基醇比他们更高的诱导对映选择性ñ，ñ在我们的催化体系双取代同类。
• METHOD OF ENANTIOSELECTIVE ADDITION TO IMINES
  申请人：National Tsing Hua University

  公开号：US20150183811A1

  公开（公告）日：2015-07-02

  The present invention relates to a method of enantioselective addition to imines, including: reacting R 2 CH═NY with R 3 ZnR 4 in the presence of a compound represented by the following formula (I), in which Y, R 1 , R 2 , R 3 and R 4 are defined the same as the specification. Accordingly, the present invention can prepare secondary amines in high yields and enantiomeric excess by the above-mentioned method.

  本发明涉及一种对亚胺进行对映选择性加成的方法，包括：在以下化合物的存在下，将R2CH═NY与R3ZnR4反应，其中该化合物由以下式（I）表示，其中Y、R1、R2、R3和R4的定义与规范相同。因此，本发明可以通过上述方法高产率和对映过量地制备二级胺。