3-phenyl-5-propionylisoxazole | 14659-66-6

• 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: 3-phenyl-5-propionylisoxazole
• 英文别名: 1-(3-phenyl-4,5-dihydro-isoxazol-5-yl)-propan-1-one；3-Phenyl-5-propionyl-Δ²-isoxazolin；1-Propanone, 1-(4,5-dihydro-3-phenyl-5-isoxazolyl)-；1-(3-phenyl-4,5-dihydro-1,2-oxazol-5-yl)propan-1-one
• CAS: 14659-66-6
• 化学式: C₁₂H₁₃NO₂
• 分子量: 203.241
• InChiKey: SGBCHKMEJQMRSN-UHFFFAOYSA-N

物化性质

• 熔点：
  43-44 °C
• 沸点：
  318.3±52.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-phenyl-5-propionylisoxazole 在 氢气 、 硼酸 、 L-Selectride 、 镍 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 8.0h， 生成 syn-3,4-dihydroxy-1-phenylhexan-1-one
  参考文献：
  名称：

  Nucleophilic additions to and reductiosn of 5-formyl-and 5-acyl-2-isoxazolines (4,5-dihydeoisoxazoles): a stereoselective route to β,γ-dihydroxy ketones

  摘要：

  Reductions of readily available 5-acyl-2-isoxazolines with L-Selectride follow the Felkin-Anh model and produce syn-5-hydroxyalkyl-2-isoxazolines with excellent (> 95:5) selectivities. Swern oxidation of 5-hydroxymethyl-2-isoxazolines, followed by direct addition of a Grignard reagent to the intermediate 5-formyl-2-isoxazolines, also follows the Felkin-Anh model and produces anti-5-hydroxyalkyl-2-isoxazolines with modest (80:20) to excellent (> 95:5) selectivity. In contrast, additions of Grignard reagents to 5-acyl-2-isoxazolines follow the chelation model, and give syn or anti products (depending on choice of acyl substituent and Grignard reagent) with good (90:10) to excellent selectivity. These selectivities are almost always far superior to those that can be obtained by direct nitrile oxide cycloaddition to a chiral allylic alcohol or ether. The resulting products are readily reduced to syn- or anti-beta,gamma-dihydroxy ketones. A speculative model to explain this surprising reversal in selectivity between formyl and acyl isoxazolines is proposed.

  DOI：

  10.1039/p19910002613
• 作为产物：
  描述：

  1-戊烯-3-酮 、 benzohydroximoyl chloride 在 三乙胺 作用下， 以 乙醚 为溶剂， 反应 6.0h， 以83%的产率得到3-phenyl-5-propionylisoxazole
  参考文献：
  名称：

  Nucleophilic additions to and reductiosn of 5-formyl-and 5-acyl-2-isoxazolines (4,5-dihydeoisoxazoles): a stereoselective route to β,γ-dihydroxy ketones

  摘要：

  Reductions of readily available 5-acyl-2-isoxazolines with L-Selectride follow the Felkin-Anh model and produce syn-5-hydroxyalkyl-2-isoxazolines with excellent (> 95:5) selectivities. Swern oxidation of 5-hydroxymethyl-2-isoxazolines, followed by direct addition of a Grignard reagent to the intermediate 5-formyl-2-isoxazolines, also follows the Felkin-Anh model and produces anti-5-hydroxyalkyl-2-isoxazolines with modest (80:20) to excellent (> 95:5) selectivity. In contrast, additions of Grignard reagents to 5-acyl-2-isoxazolines follow the chelation model, and give syn or anti products (depending on choice of acyl substituent and Grignard reagent) with good (90:10) to excellent selectivity. These selectivities are almost always far superior to those that can be obtained by direct nitrile oxide cycloaddition to a chiral allylic alcohol or ether. The resulting products are readily reduced to syn- or anti-beta,gamma-dihydroxy ketones. A speculative model to explain this surprising reversal in selectivity between formyl and acyl isoxazolines is proposed.

  DOI：

  10.1039/p19910002613

文献信息

• Palladium catalyzed C–H bond acetoxylation: isoxazolinyl as a directing group
  作者：Caiwei Geng、Minghui Jiang、Lifei Feng、Peng Jiao

  DOI：10.1039/c6ra07793e

  日期：——

  Pd(OAc)2-catalyzed acetoxylations of 3-aryl or 3-alkyl groups mounted on a 2-isoxazoline ring were studied. Ortho-selective C–H bond activation directed by an isoxazolinyl group was realized. 2-Isoxazoline rings without and with one or two alkyl substituents in the 5-position were effective directing groups. The substituent effect on reactivity and regioselectivity was examined. The acetoxylation was applied

  研究了安装在2-异恶唑啉环上的3-芳基或3-烷基的Pd（OAc）2催化的乙酰氧基化。实现了由异恶唑啉基引导的邻位选择性C–H键活化。在5-位不具有和具有一个或两个烷基取代基的2-异恶唑啉环是有效的导向基团。研究了取代基对反应性和区域选择性的影响。乙酰氧基化用于合成有用的中间体。
• A novel one-pot synthesis of hydroximoyl chlorides and 2-isoxazolines using N-tert-butyl-N-chlorocyanamide
  作者：Vinod Kumar、M.P. Kaushik

  DOI：10.1016/j.tetlet.2005.12.083

  日期：2006.2

  Treatment of aldoximes with N-tert-butyl-N-chlorocyanamide gave hydroximoyl chlorides in quantitative yields in less than a minute, which on dehydrohalogenation in the presence of triethylamine gave the corresponding nitrile oxides. The nitrile oxides underwent 1,3-dipolar addition to dipolarophiles and gave 2-isoxazolines in excellent yields under mild conditions. (c) 2005 Elsevier Ltd. All rights reserved.
• Aversa,M.C. et al., Gazzetta Chimica Italiana, 1966, vol. 96, p. 1046 - 1057
  作者：Aversa,M.C. et al.

  DOI：——

  日期：——
• Nucleophilic additions to and reductiosn of 5-formyl-and 5-acyl-2-isoxazolines (4,5-dihydeoisoxazoles): a stereoselective route to β,γ-dihydroxy ketones
  作者：Dennis P. Curran、Jaincun Zhang

  DOI：10.1039/p19910002613

  日期：——

  Reductions of readily available 5-acyl-2-isoxazolines with L-Selectride follow the Felkin-Anh model and produce syn-5-hydroxyalkyl-2-isoxazolines with excellent (> 95:5) selectivities. Swern oxidation of 5-hydroxymethyl-2-isoxazolines, followed by direct addition of a Grignard reagent to the intermediate 5-formyl-2-isoxazolines, also follows the Felkin-Anh model and produces anti-5-hydroxyalkyl-2-isoxazolines with modest (80:20) to excellent (> 95:5) selectivity. In contrast, additions of Grignard reagents to 5-acyl-2-isoxazolines follow the chelation model, and give syn or anti products (depending on choice of acyl substituent and Grignard reagent) with good (90:10) to excellent selectivity. These selectivities are almost always far superior to those that can be obtained by direct nitrile oxide cycloaddition to a chiral allylic alcohol or ether. The resulting products are readily reduced to syn- or anti-beta,gamma-dihydroxy ketones. A speculative model to explain this surprising reversal in selectivity between formyl and acyl isoxazolines is proposed.