2,4,6-Trimethyl-benzoesaeure-(2,4,6-trimethyl-benzylester) | 2004-56-0

• 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: 2,4,6-Trimethyl-benzoesaeure-(2,4,6-trimethyl-benzylester)
• 英文别名: 2,4,6-trimethylbenzyl 2,4,6-trimethylbenzoate；(2,4,6-Trimethylphenyl)methyl 2,4,6-trimethylbenzoate；(2,4,6-trimethylphenyl)methyl 2,4,6-trimethylbenzoate
• CAS: 2004-56-0
• 化学式: C₂₀H₂₄O₂
• 分子量: 296.409
• InChiKey: RAPRTANTDHHMRA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2,4,6-三甲基苯甲醛 在 bis(1,5-cyclooctadiene)nickel (0) 、 1,3-bis-(2,6-diisopropylphenyl)-4,5-dichloroimidazol-2-ylidene 作用下， 以 甲苯 为溶剂， 以84%的产率得到2,4,6-Trimethyl-benzoesaeure-(2,4,6-trimethyl-benzylester)
  参考文献：
  名称：

  Nickel-catalyzed Tishchenko reaction via hetero-nickelacycles by oxidative cyclization of aldehydes with nickel(0) complex

  摘要：

  开发了一种Ni(0)催化下的Tishchenko反应，该反应适用于多种脂肪醛（1°、2°、3°）和芳香醛。反应可能通过一个杂镍杂环中间体进行。

  DOI：

  10.1039/b926866a

文献信息

• Formamides as Lewis Base Catalysts in S_NReactions-Efficient Transformation of Alcohols into Chlorides, Amines, and Ethers
  作者：Peter H. Huy、Sebastian Motsch、Sarah M. Kappler

  DOI：10.1002/anie.201604921

  日期：2016.8.16

  and waste‐balance (E‐factor down to 2). Chiral substrates are converted with excellent levels of stereochemical inversion (99 %→≥95 % ee). In a practical one‐pot procedure, the primary formed chlorides can be further transformed into amines, azides, ethers, sulfides, and nitriles. The value of the method was demonstrated in straightforward syntheses of the drugs rac‐Clopidogrel and S‐Fendiline.

  简单的甲酰胺催化剂可促进以苯甲酰氯为唯一试剂将醇类有效转化为烷基氯。这些亲核取代是通过亚胺基活化的醇作为中间体进行的。这种新颖的方法甚至可以在无溶剂条件下进行，其特点是具有出色的官能团耐受性，可扩展性（> 100 g）和废物平衡（电子因子低至2）。手性底物的转化具有优异的立体化学转化水平（99％→≥95％ee）。在实际的一锅法中，初步形成的氯化物可以进一步转化为胺，叠氮化物，醚，硫化物和腈。该方法的价值在药物rac ‐ Clopidogrel和S‐芬迪林。
• Synthesis, Characterization, and Unique Catalytic Activities of a Fluorinated Nickel Enolate
  作者：Ryohei Doi、Kotaro Kikushima、Masato Ohashi、Sensuke Ogoshi

  DOI：10.1021/ja511730k

  日期：2015.3.11

  We have synthesized a new nickel enolate [(PhCOCF2)Ni(dcpe)][FB(C6F5)(3)] featuring fluorine atoms on the enolate moiety via B(C6F5)(3)-promoted C-F bond activation of alpha,alpha,alpha-trifluoroacetophenone. X-ray diffraction study of [(PhCOCF2)Ni(dcpe)][FB(C6F5)(3)] revealed that the complex had adopted an eta(3)-oxallyl coordination mode in the crystal lattice. The reaction of (BuNC)-Bu-t with [(PhCOCF2)Ni(dcpe)][FB(C6F5)(3)] resulted in the coordination of isocyanide to the nickel center to form a C-bound enolate complex. The reactions of [(PhCOCF2)Ni(dcpe)][FB(C6F5)(3)] with aldehydes gave insertion products quantitatively which were fully characterized by NMR spectroscopy. Furthermore, we established unique catalytic applications for [(PhCOCF2)Ni(dcpe)][FB(C6F5)(3)] toward a Tishchenko reaction, along with a highly selective crossed-esterification of alpha,alpha,alpha-trifluoroacetophenones with aldehydes.
• Nickel-Catalyzed Selective Conversion of Two Different Aldehydes to Cross-Coupled Esters
  作者：Yoichi Hoshimoto、Masato Ohashi、Sensuke Ogoshi

  DOI：10.1021/ja109908x

  日期：2011.4.6

  In the presence of a Ni(0)/NHC catalyst, an equimolar mixture of aliphatic and aryl aldehydes can be employed to selectively yield a single cross-coupled ester. This reaction can be applied to a variety of aliphatic (1 degrees, 2 degrees, cyc-2 degrees, and 3 degrees) and aryl aldehyde combinations. The reaction represents 100% atom efficiency and generates no waste. Mechanistic studies have revealed that the striking feature of the reaction is the simultaneous coordination of two aldehydes to Ni(0).