1-[2-(1,2-diphenylethenyl)phenyl]pyrazole;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;rhodium(3+);chloride | 1259203-36-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1-[2-(1,2-diphenylethenyl)phenyl]pyrazole;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;rhodium(3+);chloride
• CAS: 1259203-36-5
• 化学式: C₃₃H₃₂ClN₂Rh
• 分子量: 594.989
• InChiKey: PWSISTYDDDVDPD-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  37
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  17.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  [RhCl(phenylpyrazole)(η5-C5Me5)] 、 二苯基乙炔 以 甲醇 为溶剂， 以81%的产率得到1-[2-(1,2-diphenylethenyl)phenyl]pyrazole;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;rhodium(3+);chloride
  参考文献：
  名称：

  Alkyne insertion into cyclometallated pyrazole and imine complexes of iridium, rhodium and ruthenium; relevance to catalytic formation of carbo- and heterocycles

  摘要：

  环金属化配合物 [MCl(C⁁N)(环)]（HC⁁N = 2-苯基吡唑，M = Ir，Rh 环 = Cp*；M = Ru，环 = 对伞花烃）很容易与 RCCR 进行插入反应（ R = CO2Me, Ph) 得到单插入产物，铑配合物也与 PhCCH 区域特异性反应，得到类似的产物。环金属化亚胺配合物 [MCl(C^N)Cp*] (HC⁁N = PhCHNR, R = Ph, CH2CH2OMe, Me; M = Ir, Rh) 与 PhCCPh 的反应产物取决于取代基 R；当 R = CH2CH2OMe 时，观察到单插入，然而，对于 R = Me，初始插入产物不稳定，经历还原消除并损失有机片段，而对于 R = Ph，没有分离出含金属产物。与PhCCH一起，环金属化亚胺络合物可以得到单插入或双插入产物。讨论了串联 C-H 活化、炔插入机制催化合成碳环和杂环的影响。

  DOI：

  10.1039/c0dt00280a

文献信息

• Experimental and DFT Studies Explain Solvent Control of C–H Activation and Product Selectivity in the Rh(III)-Catalyzed Formation of Neutral and Cationic Heterocycles
  作者：David L. Davies、Charles E. Ellul、Stuart A. Macgregor、Claire L. McMullin、Kuldip Singh

  DOI：10.1021/jacs.5b04858

  日期：2015.8.5

  A range of novel heterocyclic cations have been synthesized by the Rh(III)-catalyzed oxidative C-N and C-C coupling of 1-phenylpyrazole, 2-phenylpyridine, and 2-vinyl-pyridine with alkynes (4-octyne and diphenylacetylene). The reactions proceed via initial C-H activation, alkyne insertion, and reductive coupling, and all three of these steps are sensitive to the substrates involved and the reaction conditions. Density functional theory (DFT) calculations show that C-H activation can proceed via a heteroatom-directed process that involves displacement of acetate by the neutral substrate to form charged intermediates. This step (which leads to cationic C-N coupled products) is therefore favored by more polar solvents. An alternative non-directed C-H activation is also possible that does not involve acetate displacement and so becomes favored in low polarity solvents, leading to C-C coupled products. Alkyne insertion is generally more favorable for diphenylacetylene over 4-octyne, but the reverse is true of the reductive coupling step. The diphenylacetylene moiety can also stabilize unsaturated seven-membered rhodacycle intermediates through extra interaction with one of the Ph substituents. With 1-phenylpyrazole this effect is sufficient to suppress the final C-N reductive coupling. A comparison of a series of seven-membered rhodacycles indicates the barrier to coupling is highly sensitive to the two groups involved and follows the trend C-N+ > C-N > C-C (i.e., involving the formation of cationic C-N, neutral C-N, and neutral C-C coupled products, respectively).