N-benzhydryl-3-(trifluoromethyl)pyridin-2-amine | 1416556-04-1

• 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-benzhydryl-3-(trifluoromethyl)pyridin-2-amine
• CAS: 1416556-04-1
• 化学式: C₁₉H₁₅F₃N₂
• 分子量: 328.337
• InChiKey: JDIAUZVGTVVNEL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  24.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  2-氯-3-三氟甲基吡啶 在 频哪酮 、 十二羰基三钌 、 palladium diacetate 、 potassium carbonate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 甲苯 为溶剂， 反应 40.0h， 生成 N-benzhydryl-3-(trifluoromethyl)pyridin-2-amine
  参考文献：
  名称：

  Mechanistic Investigations and Substrate Scope Evaluation of Ruthenium-Catalyzed Direct sp³ Arylation of Benzylic Positions Directed by 3-Substituted Pyridines

  摘要：

  A highly efficient direct arylation process of benzylic amines with arylboronates was developed that employs Ru catalysis. The arylation takes place with greatest efficiency at the benzylic sp(3) carbon. If the distance to the activating aryl ring is increased, arylation is still possible but the yield drops significantly. Efficiency of the CH activation was found to be significantly increased by use of 3-substituted pyridines as directing groups, which can be removed after the transformation in high yield. Calculation of the energy profile of different rotamers of the substrate revealed that presence of a substituent in the 3-position favors a conformation with the CH2 group adopting a position in closer proximity to the directing group and facilitating C-H insertion. This operationally simple reaction can be carried out in argon atmosphere as well as in air and under neutral reaction conditions, displaying a remarkable functional group tolerance. Mechanistic studies were carried out and critically compared to mechanistic reports of related transformations.

  DOI：

  10.1021/jo302547q

文献信息

• C(sp³)–H Bond Arylations Catalyzed by Well-Defined [Ru(O₂CMes)₂(<i>p</i>-cymene)]
  作者：N. Y. Phani Kumar、Rajkumar Jeyachandran、Lutz Ackermann

  DOI：10.1021/jo400658d

  日期：2013.4.19

  The well-characterized ruthenium(II) biscarboxylate complex [Ru(O2CMes)2(p-cymene)] enabled versatile direct (hetero)arylations of C(sp3)–H bonds with low (co)catalyst loading and ample substrate scope. Detailed mechanistic studies provided strong support for a facile and reversible C(sp3)–H bond metalation.

  表征充分的双羧酸钌（II）络合物[Ru（O 2 CMes）2（p- cymene）]使C（sp 3）-H键的多官能直接（杂）芳基化反应具有较低的（共）催化剂负载量和充足的底物范围。详细的力学研究为容易且可逆的C（sp 3）–H键金属化提供了有力的支持。
• Mechanistic Investigations and Substrate Scope Evaluation of Ruthenium-Catalyzed Direct sp³ Arylation of Benzylic Positions Directed by 3-Substituted Pyridines
  作者：Navid Dastbaravardeh、Karl Kirchner、Michael Schnürch、Marko D. Mihovilovic

  DOI：10.1021/jo302547q

  日期：2013.1.18

  A highly efficient direct arylation process of benzylic amines with arylboronates was developed that employs Ru catalysis. The arylation takes place with greatest efficiency at the benzylic sp(3) carbon. If the distance to the activating aryl ring is increased, arylation is still possible but the yield drops significantly. Efficiency of the CH activation was found to be significantly increased by use of 3-substituted pyridines as directing groups, which can be removed after the transformation in high yield. Calculation of the energy profile of different rotamers of the substrate revealed that presence of a substituent in the 3-position favors a conformation with the CH2 group adopting a position in closer proximity to the directing group and facilitating C-H insertion. This operationally simple reaction can be carried out in argon atmosphere as well as in air and under neutral reaction conditions, displaying a remarkable functional group tolerance. Mechanistic studies were carried out and critically compared to mechanistic reports of related transformations.