Methyl 3-(5-phenyl-4,5-dihydroisoxazol-3-yl)propionate | 86492-76-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Methyl 3-(5-phenyl-4,5-dihydroisoxazol-3-yl)propionate
• 英文别名: methyl 3-(5-phenyl-4,5-dihydroisoxazol-3-yl)propanoate；methyl 3-(5-phenyl-4,5-dihydro-3-isoxazolyl)propanoate；Methyl 3-(5-phenyl-4,5-dihydro-1,2-oxazol-3-yl)propanoate
• CAS: 86492-76-4
• 化学式: C₁₃H₁₅NO₃
• 分子量: 233.267
• InChiKey: WPIXHBLUJDWCPP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl 3-(5-phenyl-4,5-dihydroisoxazol-3-yl)propionate 在 rhodium(II) acetate dimer 作用下， 以 氯仿 为溶剂， 反应 4.0h， 生成 Dimethyl 7-oxo-3-phenyl-4-oxa-5-azatricyclo<4.3.2.0^1,5>undec-10-ene-10,11-dicarboxylate
  参考文献：
  名称：

  Synthesis of Functionalized Azomethine Ylides via the Rh(II)-Catalyzed Cyclization of .alpha.-Diazo Carbonyls onto Imino .pi.-Bonds

  摘要：

  alpha-Diazo carbonyl compounds containing an imino group in the gamma-position have been found to undergo a rhodium(II) acetate induced cyclization reaction to generate cyclic azomethine ylides. The reactive dipole undergoes a subsequent 1,3-dipolar cycloaddition with added dipolarophiles. The imino/oxime nitrogen lone pair of electrons must be properly oriented so as to interact with the rhodium carbenoid. Thus, acyclic oxime ethers which exist in the proper E-configuration readily undergo the tandem cyclization-cycloaddition reaction. In sharp contrast, the isomeric Z-oximino diazo carbonyl system does not cyclize to an azomethine ylide but rather intramolecularly inserts into the oximino C-H bond. Addition of a catalytic amount of rhodium(II) acetate to (E)-2-(diazoacetyl)benzaldehyde O-methyloxime in the presence of DMAD or N-phenylmaleimide affords a dipolar cycloadduct in high yield. When p-quinone was used as the dipolarophile, the initially formed cycloadduct was treated with acetic anhydride to give a compound containing the basic core dibenzo[a,d]cyclohepten-5,10-imine skeleton found in MK-801. Cyclic imines such as isoxazolines were particularly effective substrates for azomethine ylide formation. The rhodium(II) catalyzed reaction of 3-(4-diazo-3-oxobutyl)-5-phenyl-Delta(2)-isoxazoline with DMAD produced a 4:1 mixture of diastereomeric cycloadducts in good yield. Cyclization of the rhodium carbenoid did not occur with the aromatic isoxazole system and this is presumably due to the low basicity of the nitrogen lone pair of electrons.

  DOI：

  10.1021/jo00097a042
• 作为产物：
  描述：

  苯乙烯 、 4-硝基丁酸甲酯 在 4-二甲氨基吡啶 、 三甲基乙酰氯 、 三乙胺 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以45%的产率得到Methyl 3-(5-phenyl-4,5-dihydroisoxazol-3-yl)propionate
  参考文献：
  名称：

  脂肪族硝基化合物的串联双酰化/ [3,3]重排：通往α-氧化肟衍生物的途径。

  摘要：

  描述了硝基化合物的新的串联双酰化/重排反应。它具有广泛的底物范围，可以以高收率和区域选择性温和有效地合成α-酰氧基肟肟酯。根据获得的数据，提出了转换机制。证明了所获得的α-羟基肟酯的实用性。

  DOI：

  10.1039/c9ob01005j

文献信息

• Synthesis of 4,5-Dihydroisoxazoles by Condensation of Primary Nitro Compounds with Alkenes by Using a Copper/Base Catalytic System
  作者：Luca Cecchi、Francesco De Sarlo、Fabrizio Machetti

  DOI：10.1002/chem.200800554

  日期：2008.9.8

  A new procedure for the synthesis of 4.5-dihydroisoxazoles by condensation of primary nitro compounds with olefins by using a copper/base catalytic system is described. The catalytic effect of copper(II) salts is evidenced by comparison of the reaction rates. Thus, activated nitro compounds react faster than with organic catalysis by tertiary amines, whereas nitroalkanes, unable to condense with dipolarophiles

  描述了一种通过使用铜/碱催化体系将伯硝基化合物与烯烃缩合来合成4.5-二氢异恶唑的新方法。通过比较反应速率证明了铜（II）盐的催化作用。因此，活化的硝基化合物的反应要比叔胺的有机催化反应快，而仅在碱的存在下不能与双极性亲和剂缩合的硝基烷烃在加入铜（II）催化剂时会发生反应。在大多数反应中观察到的诱导期的出现归因于速率确定步骤之前的平衡，并暗示了拟议的反应机理。结果表明，该方法在合成实践中可能具有实用性和通用性。
• Borea; Bonora; Baraldi, Farmaco, Edizione Scientifica, 1983, vol. 38, # 6, p. 411 - 417
  作者：Borea、Bonora、Baraldi、Simoni

  DOI：——

  日期：——
• Azomethine ylide generation via the rhodium(II)-induced cyclization reaction of oximino .alpha.-diazo ketones
  作者：Albert Padwa、Dennis C. Dean

  DOI：10.1021/jo00289a001

  日期：1990.1
• Tandem double acylation/[3,3]-rearrangement of aliphatic nitro compounds: a route to α-oxygenated oxime derivatives
  作者：Yulia A. Antonova、Yulia V. Nelyubina、Alexey Yu. Sukhorukov、Sema L. Ioffe、Andrey A. Tabolin

  DOI：10.1039/c9ob01005j

  日期：——

  A new tandem double acylation/rearrangement reaction of nitro compounds is described. It has a broad substrate scope allowing the mild and efficient synthesis of α-acyloxy oxime esters in high yields and regioselectivity. According to the obtained data, the mechanism for transformation was proposed. The utility of the obtained α-hydroxy oxime esters was demonstrated.

  描述了硝基化合物的新的串联双酰化/重排反应。它具有广泛的底物范围，可以以高收率和区域选择性温和有效地合成α-酰氧基肟肟酯。根据获得的数据，提出了转换机制。证明了所获得的α-羟基肟酯的实用性。
• Synthesis of Functionalized Azomethine Ylides via the Rh(II)-Catalyzed Cyclization of .alpha.-Diazo Carbonyls onto Imino .pi.-Bonds
  作者：Albert Padwa、Dennis C. Dean、Martin H. Osterhout、Laura Precedo、Mark A. Semones

  DOI：10.1021/jo00097a042

  日期：1994.9

  alpha-Diazo carbonyl compounds containing an imino group in the gamma-position have been found to undergo a rhodium(II) acetate induced cyclization reaction to generate cyclic azomethine ylides. The reactive dipole undergoes a subsequent 1,3-dipolar cycloaddition with added dipolarophiles. The imino/oxime nitrogen lone pair of electrons must be properly oriented so as to interact with the rhodium carbenoid. Thus, acyclic oxime ethers which exist in the proper E-configuration readily undergo the tandem cyclization-cycloaddition reaction. In sharp contrast, the isomeric Z-oximino diazo carbonyl system does not cyclize to an azomethine ylide but rather intramolecularly inserts into the oximino C-H bond. Addition of a catalytic amount of rhodium(II) acetate to (E)-2-(diazoacetyl)benzaldehyde O-methyloxime in the presence of DMAD or N-phenylmaleimide affords a dipolar cycloadduct in high yield. When p-quinone was used as the dipolarophile, the initially formed cycloadduct was treated with acetic anhydride to give a compound containing the basic core dibenzo[a,d]cyclohepten-5,10-imine skeleton found in MK-801. Cyclic imines such as isoxazolines were particularly effective substrates for azomethine ylide formation. The rhodium(II) catalyzed reaction of 3-(4-diazo-3-oxobutyl)-5-phenyl-Delta(2)-isoxazoline with DMAD produced a 4:1 mixture of diastereomeric cycloadducts in good yield. Cyclization of the rhodium carbenoid did not occur with the aromatic isoxazole system and this is presumably due to the low basicity of the nitrogen lone pair of electrons.