1-(4-methoxyphenyl)-9H-carbazole | 1416353-72-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 1-(4-methoxyphenyl)-9H-carbazole
• CAS: 1416353-72-4
• 化学式: C₁₉H₁₅NO
• 分子量: 273.334
• InChiKey: QEFFLNJAECYJSH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  25
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  9-(2-pyridyl)carbazole 在 palladium diacetate 、 silver nitrate 、 对苯醌 、 三氟甲烷磺酸甲酯 作用下， 以 二氯甲烷 、 叔丁醇 为溶剂， 反应 60.0h， 生成 1-(4-methoxyphenyl)-9H-carbazole
  参考文献：
  名称：

  Direct Ortho Arylation of 9-(Pyridin-2-yl)-9H-carbazoles Bearing a Removable Directing Group via Palladium(II)-Catalyzed C–H Bond Activation

  摘要：

  A one-pot synthesis of ortho-arylated 9-(pyridin-2-yl)-9H-carbazoles via C-H bond activation is presented. Silver nitrate and tert-butyl alcohol were found to be the best oxidant and solvent for the process, respectively. The product yields are from modest to excellent, and the reaction showed sufficient functional group tolerance. p-Benzoquinone served as an important ligand for the transmetalation and reductive elimination steps in the catalytic process. The key intermediate of the reaction, a 9-(pyridin-2-yl)-9H-carbazole palladacycle, was isolated, and its structure was unequivocally confirmed by X-ray crystallography. No kinetic isotope effect (k(H)/k(D) = 1.00 +/- 0.17) for the C-H bond activation step was observed. In addition, a Hammett experiment gave a negative rho value, -2.16 +/- 0.02. The directing group, pyridinyl, was demonstrated to be a removable functional group. Finally, a rational catalytic mechanism is presented on the basis of all experimental evidence.

  DOI：

  10.1021/om301071m

文献信息

• Silver(I)- or Copper(II)-Mediated Dearomatization of Aromatic Ynones: Direct Access to Spirocyclic Scaffolds
  作者：Michael J. James、James D. Cuthbertson、Peter O'Brien、Richard J. K. Taylor、William P. Unsworth

  DOI：10.1002/anie.201501812

  日期：2015.6.22

  A high‐yielding silver(I)‐ or copper(II)‐catalyzed dearomatizing spirocyclization strategy allows the conversion of simple aromatic compounds that contain ynone substituents, including indole, anisole, pyrrole, and benzofuran derivatives, into functionalized spirocyclic scaffolds. A high‐yielding asymmetric variant furnishes spirocyclic indolenines in up to 89:11 e.r.

  一种高产的银（I）或铜（II）催化的脱芳构螺环化策略可以将含有ynone取代基的简单芳族化合物（包括吲哚，苯甲醚，吡咯和苯并呋喃衍生物）转化为功能化的螺环骨架。一种高产的不对称变异体，可在高达89:11 er的温度下提供螺环吲哚胺
• Bismuth(III) Triflate Catalyzed Three-Component Reactions of Indoles, Ketones, and α-Bromoacetaldehyde Acetals Enable Indole-to-Carbazole Transformation
  作者：Yanlong Gu、Wenbo Huang、Shaomin Chen、Xin Wang

  DOI：10.1021/acs.orglett.8b01707

  日期：2018.7.20

  A three-component reaction of indoles, α-bromoacetaldehyde acetals, and ketones was developed by using bismuth(III) triflate as the catalyst to realize a straightforward approach for synthesizing carbazole derivatives. The reaction was established mechanistically through the autotandem catalysis of Bi(OTf)3 in the following two steps: (i) Friedel–Crafts-type alkylation of indole with α-bromoacetaldehyde

  以三氟甲磺酸铋（III）为催化剂，开发了吲哚，α-溴乙醛缩醛和酮的三组分反应，从而实现了咔唑衍生物的直接合成方法。该反应是通过以下两个步骤通过Bi（OTf）3的自动串联机理以机械方式建立的：（i）吲哚与α-溴乙醛缩醛的Friedel-Crafts型烷基化反应，产生了一种三乙醛型中间体，以及（ii）[ [4 + 2]将此中间体与酮组分环合。
• Temporary (PO) directing group enabled carbazole <i>ortho</i> arylation <i>via</i> palladium catalysis
  作者：Zhi-Chao Qi、Qin-Xin Lou、Yuan Niu、Shang-Dong Yang

  DOI：10.1039/d0cc07596e

  日期：——

  A palladium-catalyzed, temporary P(O) directing group assisted C–H bond arylation of carbazoles was achieved. The release of the directing group occurs spontaneously in the reaction and the mechanistic studies indicate that acid is essential for N–P bond cleavage.

  实现了钯催化的临时P（O）导向基团协助咔唑的C–H键芳基化。引导基团的释放是在反应中自发发生的，并且机理研究表明，酸对于N-P键的裂解至关重要。
• Direct Ortho Arylation of 9-(Pyridin-2-yl)-9<i>H</i>-carbazoles Bearing a Removable Directing Group via Palladium(II)-Catalyzed C–H Bond Activation
  作者：Jean-Ho Chu、Chung-Chiu Wu、Deng-Hsiang Chang、Ya-Ming Lee、Ming-Jung Wu

  DOI：10.1021/om301071m

  日期：2013.1.14

  A one-pot synthesis of ortho-arylated 9-(pyridin-2-yl)-9H-carbazoles via C-H bond activation is presented. Silver nitrate and tert-butyl alcohol were found to be the best oxidant and solvent for the process, respectively. The product yields are from modest to excellent, and the reaction showed sufficient functional group tolerance. p-Benzoquinone served as an important ligand for the transmetalation and reductive elimination steps in the catalytic process. The key intermediate of the reaction, a 9-(pyridin-2-yl)-9H-carbazole palladacycle, was isolated, and its structure was unequivocally confirmed by X-ray crystallography. No kinetic isotope effect (k(H)/k(D) = 1.00 +/- 0.17) for the C-H bond activation step was observed. In addition, a Hammett experiment gave a negative rho value, -2.16 +/- 0.02. The directing group, pyridinyl, was demonstrated to be a removable functional group. Finally, a rational catalytic mechanism is presented on the basis of all experimental evidence.