4,4-dimethyl-2-(2-(trimethylsilyl)phenyl)-4,5-dihydrooxazole

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 4,4-dimethyl-2-(2-(trimethylsilyl)phenyl)-4,5-dihydrooxazole
• 英文别名: [2-(4,4-dimethyl-5H-1,3-oxazol-2-yl)phenyl]-trimethylsilane
• 化学式: C₁₄H₂₁NOSi
• 分子量: 247.412
• InChiKey: KHXGMHXBWVWAAC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.79
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4-dimethyl-2-(2-(trimethylsilyl)phenyl)-4,5-dihydrooxazole 在 chromium dichloride 、 2,3-二氯丁烷 、 一氯化碘 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 9.0h， 生成 2-(4'-fluoro-3-iodo-[1,1'-biphenyl]-2-yl)-4,4-dimethyl-4,5-dihydrooxazole
  参考文献：
  名称：

  Room-Temperature Chromium(II)-Catalyzed Direct Arylation of Pyridines, Aryl Oxazolines, and Imines Using Arylmagnesium Reagents

  摘要：

  We report a CrCl2 catalyzed oxidative arylation of various pyridines, aryl oxazolines, and aryl imines using aromatic Grignard reagent in the presence of 2,3-dichlor-obutane (DCB). Most of the reaction proceed rapidly at 25 degrees C and do not require any additional ligand Benzo[h] quinoline, 2-arylpyridine, aryl oxazoline, and imines were successfully arylated in good yields under these conditions. A TMS-substituent was used to prevent double arylation. After oxidative cross-coupling the TMS-group was further converted to a second ortho-aryl substituent. Remarkably, inexpensive aryl N-butylimine derivatives are excellent substrate for this oxidative arylation.

  DOI：

  10.1021/ol502623v
• 作为产物：
  描述：

  三甲基氯硅烷 、 4,4-二甲基-2-苯基-2-噁唑啉 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 3.75h， 以56%的产率得到4,4-dimethyl-2-(2-(trimethylsilyl)phenyl)-4,5-dihydrooxazole
  参考文献：
  名称：

  Room-Temperature Chromium(II)-Catalyzed Direct Arylation of Pyridines, Aryl Oxazolines, and Imines Using Arylmagnesium Reagents

  摘要：

  We report a CrCl2 catalyzed oxidative arylation of various pyridines, aryl oxazolines, and aryl imines using aromatic Grignard reagent in the presence of 2,3-dichlor-obutane (DCB). Most of the reaction proceed rapidly at 25 degrees C and do not require any additional ligand Benzo[h] quinoline, 2-arylpyridine, aryl oxazoline, and imines were successfully arylated in good yields under these conditions. A TMS-substituent was used to prevent double arylation. After oxidative cross-coupling the TMS-group was further converted to a second ortho-aryl substituent. Remarkably, inexpensive aryl N-butylimine derivatives are excellent substrate for this oxidative arylation.

  DOI：

  10.1021/ol502623v

文献信息

• Rhodium-Catalyzed Si-F Exchange Reaction between Fluorobenzenes and a Disilane. Catalytic Reaction Involving Cleavage of C-F Bonds
  作者：Yutaka Ishii、Naoto Chatani、Shuhei Yorimitsu、Shinji Murai

  DOI：10.1246/cl.1998.157

  日期：1998.2

  The reaction of functionalized fluorobenzenes, such as fluoroacetophenones and (fluorophenyl)oxazolines, with Me3SiSiMe3 in the presence of a catalytic amount of a rhodium complex results in a site-selective Si-F exchange to give ortho-(trimethylsilyl)fluorobenzenes. The reaction involves cleavage of C-F bonds.

  在催化量的铑配合物存在下，功能化的氟苯（例如氟代苯乙酮和（氟苯基）恶唑啉）与 Me3SiSiMe3 的反应导致位点选择性 Si-F 交换，得到邻（三甲基甲硅烷基）氟苯。该反应涉及 CF 键的断裂。
• Direct Carbonylation at a C−H Bond in the Benzene Ring of 2-Phenyloxazolines Catalyzed by Ru₃(CO)₁₂. Scope, Limitations, and Mechanistic Aspects
  作者：Yutaka Ie、Naoto Chatani、Takashi Ogo、Daniel R. Marshall、Takahide Fukuyama、Fumitoshi Kakiuchi、Shinji Murai

  DOI：10.1021/jo991660t

  日期：2000.3.1

  The ruthenium-catalyzed carbonylation at a C-H bond in the benzene ring of a 2-phenyloxazoline is described. The reaction of 2-phenyloxazolines with CO and ethylene in toluene in the presence of a catalytic amount of Ru-3(CO)(12) resulted in propionylation at an ortho C-H bond in the benzene ring. The presence of the oxazoline ring on the benzene ring is essential for the carbonylation to proceed. Other heterocycles, such as oxazine, oxazole, and thiazoline rings, also served as acceptable directing groups as did the oxazoline ring. A wide functional group compatibility was observed. The site selectivity of the carbonylation was examined using meta-substituted phenyloxazolines. It was found that the carbonylation took place exclusively at the less-hindered C-H bond, irrespective of the nature of substituents, indicating that the site selectivity was determined by steric factors. The reaction was also applicable, not only to a benzene ring, but also to naphthyl and thiophenyl rings. Olefins such as propene and trimethylvinylsilane in place of ethylene could also be used in the carbonylation reaction, while other olefins, such as l-hexene, tert-butylethylene, vinylcyclohexane, isoprene, 1,5-hexadiene, cyclohexene, 1,5-cyclooctadiene, styrene, methyl acrylate, vinyl acetate, allyltrimethylsilane, and triethoxyvinylsilane did not afford the coupling products. An equilibrium between 2-phenyloxazolines, carbon monoxide, and olefins exists on one hand and the corresponding ketones on the other hand, and product composition is governed by the equilibrium thermodynamics of the system. The results of deuterium labeling experiments suggest that the catalysis involves a reversible C-H bond cleavage and that the rate-determining step is not the cleavage of a C-H bond. The results of kinetic study of the effects of CO pressure show that the reaction rate accelerates with decreasing CO pressure.
• CHRISTIAENS, L.;LUXEN, A.;EVERS, M.;THIBAUT, PH.;MBUYI, M.;WELTER, A., CHEM. SCR., 1984, 24, N 4-5, 178-184
  作者：CHRISTIAENS, L.、LUXEN, A.、EVERS, M.、THIBAUT, PH.、MBUYI, M.、WELTER, A.

  DOI：——

  日期：——
• Room-Temperature Chromium(II)-Catalyzed Direct Arylation of Pyridines, Aryl Oxazolines, and Imines Using Arylmagnesium Reagents
  作者：Olesya M. Kuzmina、Paul Knochel

  DOI：10.1021/ol502623v

  日期：2014.10.3

  We report a CrCl2 catalyzed oxidative arylation of various pyridines, aryl oxazolines, and aryl imines using aromatic Grignard reagent in the presence of 2,3-dichlor-obutane (DCB). Most of the reaction proceed rapidly at 25 degrees C and do not require any additional ligand Benzo[h] quinoline, 2-arylpyridine, aryl oxazoline, and imines were successfully arylated in good yields under these conditions. A TMS-substituent was used to prevent double arylation. After oxidative cross-coupling the TMS-group was further converted to a second ortho-aryl substituent. Remarkably, inexpensive aryl N-butylimine derivatives are excellent substrate for this oxidative arylation.