(+/-)-3-buten-2-yl 4-methoxybenzoate

• 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-buten-2-yl 4-methoxybenzoate
• 英文别名: but-3-en-2-yl 4-methoxybenzoate
• 化学式: C₁₂H₁₄O₃
• 分子量: 206.241
• InChiKey: NSBNUVWAYVCEQO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.43
• 重原子数：
  15.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  N-hydroxy-4-methylbenzenecarboximidoyl chloride 、 (+/-)-3-buten-2-yl 4-methoxybenzoate 在 三乙胺 作用下， 以 乙醚 为溶剂， 以46%的产率得到(5RS)-5-[(1RS)-1-anisoyloxyethyl]-3-p-methylphenyl-2-isoxazoline
  参考文献：
  名称：

  氮氧化物对各种外消旋3-酰氧基和3-羟基丁-1-烯的[3 + 2]环加成反应的区域和立体选择性研究

  摘要：

  芳基腈氧化物2d-f与各种外消旋的3-羟基和3-酰氧基-丁-1-烯1a-c的1,3-偶极环加成反应具有完全的区域选择性，从而以良好的收率提供了相应的3,5-二取代的异恶唑啉。已经研究了烯丙基位置上的酰氧基对立体选择性的空间和/或电子效应。

  DOI：

  10.2174/157017812800221681
• 作为产物：
  描述：

  3-丁烯-2-醇 、 对甲氧基苯甲酰氯 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以79%的产率得到(+/-)-3-buten-2-yl 4-methoxybenzoate
  参考文献：
  名称：

  Kinetic Resolution by Enantioselective Dihydroxylation of Secondary Allylic 4-Methoxybenzoate Esters Using a Mechanistically Designed Cinchona Alkaloid Catalyst

  摘要：

  The OsO4-cinchona alkaloid catalyzed asymmetric dihydroxylation process has been applied successfully to the kinetic resolution of 1-substituted allylic alcohols by the use of the 4-methoxybenzoyl derivatives in conjunction with the specifically designed DHQD-PYDZ(S)-anthryl catalyst (5 . OsO4). Thus, (+/-)-3-buten-2-yl 4-methoxybenzoate (4a) and (+/-)-1-phenyl-2-propen-1-yl 4-methoxybenzoate (4b) have been kinetically resolved with relative rate constants of 20 and 79, respectively. These values are among the best reported for the kinetic resolution of racemic compounds using non-enzymatic catalyst systems. The design of this resolution process was accomplished under mechanistic guidance using the transition state model proposed recently for the asymmetric dihydroxylation process. The specially selected ligand 5 possesses a deep U-shaped binding pocket with both the methoxyquinoline and the 1-anthryl walls projecting rearward of the pyridazine linker group at the floor. This catalyst not only recognizes the 4-methoxybenzoyl group of these substrates, which extends into the distant binding pocket of the catalyst, but also provides an open space adjacent to one of the allylic alpha-substituents of the substrate which allows for enantiomeric selection in the dihydroxylation. The magnitude of the kinetic resolution and the absolute stereopreference for the dihydroxylation reaction provide strong evidence for the guiding mechanistic model. The utility of this process is clearly demonstrated by the selective dihydroxylation of 1,4-pentadien-3-yl 4-methoxybenzoate (10) to give diol 11 in 70% isolated yield with >98% ee and >96% de.

  DOI：

  10.1021/ja00149a004

文献信息

• Kinetic Resolution by Enantioselective Dihydroxylation of Secondary Allylic 4-Methoxybenzoate Esters Using a Mechanistically Designed Cinchona Alkaloid Catalyst
  作者：E. J. Corey、Mark C. Noe、Angel Guzman-Perez

  DOI：10.1021/ja00149a004

  日期：1995.11

  The OsO4-cinchona alkaloid catalyzed asymmetric dihydroxylation process has been applied successfully to the kinetic resolution of 1-substituted allylic alcohols by the use of the 4-methoxybenzoyl derivatives in conjunction with the specifically designed DHQD-PYDZ(S)-anthryl catalyst (5 . OsO4). Thus, (+/-)-3-buten-2-yl 4-methoxybenzoate (4a) and (+/-)-1-phenyl-2-propen-1-yl 4-methoxybenzoate (4b) have been kinetically resolved with relative rate constants of 20 and 79, respectively. These values are among the best reported for the kinetic resolution of racemic compounds using non-enzymatic catalyst systems. The design of this resolution process was accomplished under mechanistic guidance using the transition state model proposed recently for the asymmetric dihydroxylation process. The specially selected ligand 5 possesses a deep U-shaped binding pocket with both the methoxyquinoline and the 1-anthryl walls projecting rearward of the pyridazine linker group at the floor. This catalyst not only recognizes the 4-methoxybenzoyl group of these substrates, which extends into the distant binding pocket of the catalyst, but also provides an open space adjacent to one of the allylic alpha-substituents of the substrate which allows for enantiomeric selection in the dihydroxylation. The magnitude of the kinetic resolution and the absolute stereopreference for the dihydroxylation reaction provide strong evidence for the guiding mechanistic model. The utility of this process is clearly demonstrated by the selective dihydroxylation of 1,4-pentadien-3-yl 4-methoxybenzoate (10) to give diol 11 in 70% isolated yield with >98% ee and >96% de.
• Study of the Regio- and Stereoselectivity of [3+2] Cycloaddition of Nitrile Oxides to Various Racemic 3-acyloxy and 3-hydroxybut-1-enes
  作者：Heithem Abda、Kaiss Aouadi、David Gueyrard、Jean-Pierre Praly、Moncef Msaddek

  DOI：10.2174/157017812800221681

  日期：2012.2.1

  1,3-Dipolar cycloadditions of aryl nitrile oxides 2d-f to various racemic 3-hydroxy- and 3-acyloxy-but-1-enes 1a-c proceeded with complete regioselectivity to afford the corresponding 3,5-disubstituted isoxazolines in good yields. The steric and/or electronic effect of an acyloxy group at the allylic position on the stereoselectivity has been studied.

  芳基腈氧化物2d-f与各种外消旋的3-羟基和3-酰氧基-丁-1-烯1a-c的1,3-偶极环加成反应具有完全的区域选择性，从而以良好的收率提供了相应的3,5-二取代的异恶唑啉。已经研究了烯丙基位置上的酰氧基对立体选择性的空间和/或电子效应。