(+/-)-ethyl cis-3a,4,5,6,7,7a-hexahydrocyclohexaisoxazole-3-carboxylate | 83967-93-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: (+/-)-ethyl cis-3a,4,5,6,7,7a-hexahydrocyclohexaisoxazole-3-carboxylate
• 英文别名: ethyl 3a,4,5,6,7,7a-hexahydrobenzo[d]isoxazole-3-carboxylate；ethyl cis-3a,4,5,6,7,7a-hexahydrobenzo[d]isoxazole-3-carboxylate
• CAS: 83967-93-5
• 化学式: C₁₀H₁₅NO₃
• 分子量: 197.234
• InChiKey: AEFNIXMBTVAXMG-SFYZADRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.49
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  47.89
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (+/-)-ethyl cis-3a,4,5,6,7,7a-hexahydrocyclohexaisoxazole-3-carboxylate 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 生成 (3aS,7aS)-1-(3a,4,5,6,7,7a-Hexahydro-benzo[d]isoxazol-3-yl)-methanol
  参考文献：
  名称：

  Nitrile oxides in medicinal chemistry. 6. Enzymatic resolution of a set of bicyclic Δ2-isoxazolines

  摘要：

  Chymotrypsin selectively catalyzed the hydrolysis of a series of 3-ethoxycarbonyl-Delta(2)-isoxazolines 1-4, whereas lipase from Pseudomonas cepacia (lipase PS) was remarkably selective in hydrolysing the corresponding 3-hydroxymethyl-Delta(2)-isoxazoline butyrates (5-8). The enantio-preference of chymotrypsin for the first set of compounds is the same as that observed for the lipase PS-cataiyzed hydrolysis of the other series of substrates. The hydrolytic activity of lipase PS for compounds 5-8 was considerably higher than that shown by chymotrypsin for substrates 1-4. (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0957-4166(96)00075-4
• 作为产物：
  描述：

  氯代肟基乙酸乙酯 、 环己烯 在 碳酸氢钠 作用下， 以 乙酸乙酯 为溶剂， 以56 %的产率得到(+/-)-ethyl cis-3a,4,5,6,7,7a-hexahydrocyclohexaisoxazole-3-carboxylate
  参考文献：
  名称：

  螺环和稠合异恶唑啉砌块的合成

  摘要：

  公开了一种通过功能化的氯肟和环烯烃的 1,3-偶极环加成合成稠合和螺环sp 3富集异恶唑啉结构单元的可扩展且有效的方法。目标化合物以多克规模制备，并揭示了它们进一步功能化的潜力。

  DOI：

  10.1002/ejoc.202300282

文献信息

• Water-Assisted Nitrile Oxide Cycloadditions: Synthesis of Isoxazoles and Stereoselective Syntheses of Isoxazolines and 1,2,4-Oxadiazoles
  作者：Chatchai Kesornpun、Thammarat Aree、Chulabhorn Mahidol、Somsak Ruchirawat、Prasat Kittakoop

  DOI：10.1002/anie.201511730

  日期：2016.3.14

  Conventional methods generate nitrile oxides from oxime halides in organic solvents under basic conditions. However, the present work revealed that water‐assisted generation of nitrile oxides proceeds under mild acidic conditions (pH 4–5). Cycloadditions of nitrile oxides with alkynes and alkenes easily occurred in water without using catalysts, thus yielding isoxazoles and isoxazolines, respectively

  常规方法是在碱性条件下由有机溶剂中的肟卤化物生成腈氧化物。但是，目前的工作表明，在弱酸性条件下（pH值为4-5）会进行水辅助生成的腈氧化物。在不使用催化剂的情况下，腈类化合物与炔烃和烯烃的环加成反应很容易在水中发生，因此分别制得异恶唑和异恶唑啉，对五元和六元环状烯烃具有出色的立体选择性。还实现了两个单元的腈与环己烯的双立体选择性环加成反应，从而得到具有独特的异恶唑啉-恶二唑骨架的1,2,4-恶二唑衍生物。从具有环应变的单萜制备对映体纯的异恶唑啉。在一种情况下，仅制备了蝴蝶状结构的异恶唑啉，
• Methods for the stereoselective cis-cyanohydroxylation and -carboxyhydroxylation of olefins
  作者：Alan P. Kozikowski、Maciej Adamcz

  DOI：10.1021/jo00151a017

  日期：1983.2
• Resolution of ?2-isoxazoline-5-carboxylates by a protease fromAspergillus Oryzae providing masked synthons for enantiopure ?-aminoalcohols and related structures
  作者：S. Yang、W. Hayden、H. Griengl

  DOI：10.1007/bf00811865

  日期：1994.4

  A series of racemic DELTA2-isoxazolinecarboxylates have been synthesized and subjected to enzymatic hydrolysis by a protease from Aspergillus oryzae in a two-phase system. Out of these compounds only isoxazoline-5-carboxylates unsubstituted at C-4 were hydrolyzed. Thus, from 3-ethoxycarbonyl-, 3-methyl-, and 3-phenyl-DELTA2-isoxazoline-5-carboxylates the corresponding (R)-configurated carboxylic acids are obtained. In contrast, an additional methyl group at C-5 changes the steric course of the hydrolysis to give predominantly the (S)-acid. The enantioselectivities obtained are in the range of E = 5-35.