4,5-diphenylpyrazolo[1,5-a]quinoline | 1260140-60-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 4,5-diphenylpyrazolo[1,5-a]quinoline
• CAS: 1260140-60-0
• 化学式: C₂₃H₁₆N₂
• 分子量: 320.393
• InChiKey: VAYRTVFCDKRSDN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 4,5-diphenylpyrazolo[1,5-a]quinoline 在 sodium acetate 作用下， 以 甲醇 为溶剂， 反应 16.0h， 以70%的产率得到
  参考文献：
  名称：

  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

  摘要：

  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).

  DOI：

  10.1021/jacs.5b04858
• 作为产物：
  描述：

  3-苯雪梨酮 在 dipotassium peroxodisulfate 、 dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 copper diacetate 作用下， 以 1,2-二氯乙烷 、 乙腈 为溶剂， 反应 34.0h， 生成 4,5-diphenylpyrazolo[1,5-a]quinoline
  参考文献：
  名称：

  铑催化氧化合成喹啉融合的Sydnones通过2倍CH键的活化

  摘要：

  Rh（III）催化的中性离子杂环的合成是通过Synonnon的C–H活化和与内部炔烃的氧化偶联而实现的。该反应在温和的条件下以高效率，较宽的底物范围和较低的催化剂负载量进行。此外，已在后期衍生化为各种高度功能化的支架中证明了偶联产物的合成应用。

  DOI：

  10.1021/acs.joc.6b02356

文献信息

• Rhodium-Catalyzed Oxidative 1:1, 1:2, and 1:4 Coupling Reactions of Phenylazoles with Internal Alkynes through the Regioselective Cleavages of Multiple C−H Bonds
  作者：Nobuyoshi Umeda、Koji Hirano、Tetsuya Satoh、Naoto Shibata、Hirofumi Sato、Masahiro Miura

  DOI：10.1021/jo1021184

  日期：2011.1.7

  selectively through the coupling of 1-phenylpyrazole and diphenylacetylene in 1:1, 1:2, and 1:4 manners, respectively. The reactions preferentially take place at the electron-deficient sites on the aromatic substrates. A comparison of reactivities of variously substituted and deuterated substrates sheds light on the mechanism of C−H bond cleavage steps. The reaction pathway is highly dependent on reaction

  在铑催化剂和铜氧化剂伴有双或四键CH键断裂的情况下，苯唑与内部炔烃的直接氧化偶联有效地进行。因此，作为代表性的例子，4,5-二苯基吡唑并[1,5- a]喹啉，1-（1,2,3,4-四苯基萘-5-基）吡唑和1-（1,2,3,4,5,6,7,8-八苯基蒽-9-基）吡唑可以通过分别以1：1、1：2和1：4的方式通过1-苯基吡唑和二苯基乙炔的偶合来选择性获得。该反应优选在芳族底物上的电子不足的位置发生。各种取代和氘代底物的反应性比较揭示了CH键断裂步骤的机理。反应路径高度依赖于所采用的反应条件，特别是取决于溶剂的性质。关键的rhodocycle中间体的溶剂化的影响已进行了计算研究。另外，已经发现一些稠合的芳族产物在固态下表现出强烈的荧光。
• Rhodium-Catalyzed Oxidative Synthesis of Quinoline-Fused Sydnones via 2-fold C–H Bond Activation
  作者：Lei Li、He Wang、Xifa Yang、Lingheng Kong、Fen Wang、Xingwei Li

  DOI：10.1021/acs.joc.6b02356

  日期：2016.12.2

  Rh(III)-catalyzed synthesis of mesoionic heterocycles has been achieved via C–H activation of sydnones and oxidative coupling with internal alkynes. This reaction occurred under mild conditions with high efficiency, broad substrate scope, and low catalyst loading. Moreover, synthetic applications of a coupled product have been demonstrated in the late-stage derivatization into a variety of highly functionalized

  Rh（III）催化的中性离子杂环的合成是通过Synonnon的C–H活化和与内部炔烃的氧化偶联而实现的。该反应在温和的条件下以高效率，较宽的底物范围和较低的催化剂负载量进行。此外，已在后期衍生化为各种高度功能化的支架中证明了偶联产物的合成应用。
• 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).