4,4-dimethyl-3-phenyl-2-isoxazoline-5-methanol | 141525-33-9

• 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: 4,4-dimethyl-3-phenyl-2-isoxazoline-5-methanol
• 英文别名: (4,4-dimethyl-3-phenyl-4,5-dihydroisoxazol-5-yl)methanol；(4,4-dimethyl-3-phenyl-5H-1,2-oxazol-5-yl)methanol
• CAS: 141525-33-9
• 化学式: C₁₂H₁₅NO₂
• 分子量: 205.257
• InChiKey: OTXBKLUXNKYODP-UHFFFAOYSA-N

物化性质

• 沸点：
  308.6±34.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  41.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (E)-2,2-dimethyl-1-phenylbut-3-en-1-one oxime 在 叔丁基过氧化氢 、 Co(nmp)₂ 、 氧气 作用下， 以 水 、 异丙醇 为溶剂， 55.0 ℃ 、101.33 kPa 条件下， 反应 5.0h， 以77%的产率得到4,4-dimethyl-3-phenyl-2-isoxazoline-5-methanol
  参考文献：
  名称：

  钴催化的β，γ-不饱和肟的好氧氧化环化

  摘要：

  钴配合物Co（nmp）2可以有效催化β，γ-不饱和肟的有氧氧化5-外切环化反应，得到异恶唑啉。关键的环化步骤涉及碳中心自由基的产生。产物在很大程度上取决于反应条件。当在i -PrOH中进行反应时，主要产生氧化终止产物2，而在环己-1,4-二烯存在下，在甲苯中选择性地获得还原终止产物3。

  DOI：

  10.1016/j.tet.2013.02.032

文献信息

• Palladium-Catalyzed Oxime Assisted Intramolecular Dioxygenation of Alkenes with 1 atm of Air as the Sole Oxidant
  作者：Ming-Kui Zhu、Jun-Feng Zhao、Teck-Peng Loh

  DOI：10.1021/ja100716x

  日期：2010.5.12

  This paper describes a palladium-catalyzed oxime assisted intramolecular dioxygenation of alkenes by using 1 atm of air as the sole oxidant under extremely mild conditions, which demonstrated the feasibility of incorporating atmospheric oxygen into synthetically useful products under 1 atm of air at room temperature.
• Regiocontrol of nitrile oxide cycloadditions to allyl alcohols. Synthesis of 4-substituted and 4,4-disubstituted 5-hydroxymethyl-2-isoxazolines
  作者：Shuji Kanemasa、Masaki Nishiuchi、Eiji Wada

  DOI：10.1016/s0040-4039(00)91622-8

  日期：1992.3

  The first regiocontrol of nitrile oxide cycloadditions is described. Reaction of benzonitrile oxide with (E)-2-butenol is highly accelerated by the presence of a magnesium alkoxide, and this reaction proceeds in an exclusively regioselective manner to produce 5-hydroxymethyl-4-methyl-3-phenyl-2-isoxazoline as the sole cycloadduct. Synthetic applications to other substituted allyl alcohols are discussed.
• First Successful Metal Coordination Control in 1,3-Dipolar Cycloadditions. High-Rate Acceleration and Regio- and Stereocontrol of Nitrile Oxide Cycloadditions to the Magnesium Alkoxides of Allylic and Homoallylic Alcohols
  作者：Shuji Kanemasa、Masaki Nishiuchi、Akio Kamimura、Kenzi Hori

  DOI：10.1021/ja00085a012

  日期：1994.3

  The first successful control of stereo- and regioselectivity in 1,3-dipolar cycloadditions by metal coordination is described. The presence of magnesium ions dramatically accelerates nitrile oxide dipolar cycloadditions to allylic alcohols, improving both the regio- and stereoselectivity of the reaction. For example, cycloadditions to terminal allylic alcohols bearing alpha-chirality produce syn-stereoisomers of 2-isoxazolines selectively, and reactions involving the magnesium alkoxides of internal allylic alcohols are exclusively regioselective in favor of 5-hydroxymethyl-2-isoxazolines. Metal alkoxides other than magnesium, such as lithium, zinc, and aluminum alkoxides, are less effective. These reactions involve the formation of activated intermediates in which a nitrile oxide and an allylic alkoxide coordinate to the magnesium ion. Theoretical calculations indicate that the formation of the coordinated intermediates enhances the rate of cycloaddition and also improves the syn-selectivity.