(5S)-(+)-3,5-diphenyl-4,5-dihydro-isoxazole | 20080-12-0

• 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: (5S)-(+)-3,5-diphenyl-4,5-dihydro-isoxazole
• 英文别名: 3,5-Diphenyl-4,5-dihydro-isoxazol；(S)-3,5-diphenyl-2-isoxazoline；3,5-diphenyl-4,5-dihydro-isoxazole；(5S)-3,5-diphenyl-4,5-dihydro-1,2-oxazole
• CAS: 20080-12-0
• 化学式: C₁₅H₁₃NO
• 分子量: 223.274
• InChiKey: JNTURVIUZIGWEQ-HNNXBMFYSA-N

物化性质

• 熔点：
  83.7-84.2 °C(Solv: hexane (110-54-3); dichloromethane (75-09-2))
• 沸点：
  351.4±45.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (5S)-(+)-3,5-diphenyl-4,5-dihydro-isoxazole 在 sodium tetrahydroborate 、 nickel dichloride 作用下， 以 乙醇 为溶剂， 反应 21.0h， 生成
  参考文献：
  名称：

  Asymmetric reduction of racemic 2-isoxazolines

  摘要：

  The kinetic resolution of racemic 2-isoxazolines was carried out by asymmetric reduction using borane with 1,2-amino alcohols as a chiral Source. Using excess BH3-THF in the presence of (-)-norephedrine, optically active 1,3-amino alcohol derivatives were obtained with good ee but in lower yield, while the optically active substrates 2-isoxazolines were recovered with modest ee. The asymmetric reduction using 2.0 equiv of BH3-SMe2 was investigated as an alternative strategy for the synthesis of optically active products. After reduction, treatment of the resulting Mixture with Et3N was successful in providing optically active isoxazolidine derivatives in good yields and with good ee. The choice of chiral source was also shown to have a significant effect. In particular, the use of (S)-alpha,alpha-diphenyl-2-pyrrolidinemethanol reversed the enantioselectivity of the recovered Substrates. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2008.11.005
• 作为产物：
  描述：

  (3R)-(+)-1,3-diphenyl-3-phenylsulfanylpropan-1-one 在 羟胺 、 sodium hydride 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 (5S)-(+)-3,5-diphenyl-4,5-dihydro-isoxazole
  参考文献：
  名称：

  通过氧和氮亲核试剂分子内取代噻吩氧化物的闭环反应：4,5-二氢异恶唑和4,5-二氢吡唑的简单立体定向合成

  摘要：

  报道了一种新的，简单的方法，该方法可以从苯硫酚的手性迈克尔加合物向查耳酮的易获得的肟中立体定向合成3,5-二取代的4,5-二氢-异恶唑（手性异恶唑啉）。与迈克尔加成物的N-芳基hydr类似的反应得到非外消旋的1-（芳基）-3,5-二苯基-4,5-二氢-1H-吡唑（手性吡唑啉），但是这些产物构型不稳定。合成的关键步骤是闭环反应，该反应通过噻吩氧化物的立体特异性分子内亲核取代而发生。

  DOI：

  10.1016/j.tet.2005.03.085

文献信息

• Enhanced asymmetric induction in cycloadditions to bridgehead-chiral vinyl dioxazaborocines
  作者：Christopher D Davies、Stephen P Marsden、Elaine S.E Stokes

  DOI：10.1016/s0040-4039(00)00571-2

  日期：2000.5

  Vinyl dioxazaborocines 5 with asymmetric centres on the nitrogen bridgehead substituent have been prepared and assayed in nitrile oxide and nitrone cycloadditions, giving asymmetric inductions of up to 70 and 74% ee, respectively.

  制备了在氮桥头取代基上具有不对称中心的乙烯基二恶杂硼硼烷5，并在一氧化二氮和硝酮环加成中进行了分析，分别得出不对称诱导率分别为70％和74％ee。
• Chiral differentiation of novel isoxazoline derivatives on “clicked” thioether and triazole bridged cyclodextrin chiral stationary phases
  作者：Xiaobin Yao、Yan Gong、Rehangu Mamuti、Wenwen Xing、Hao Zheng、Xiangyang Tang、Yong Wang

  DOI：10.1039/c4ra03476g

  日期：——

  Isoxazoline derivatives have been disclosed in the art as having acaricidal and insecticidal activity and as potential precursors for the syntheses of natural products. This work first demonstrates the chiral resolution of isoxazoline derivatives that had not been studied before on native cyclodextrin (CD) chiral stationary phases (CSPs). Two structurally well-defined CSPs based on native CD were prepared

  异恶唑啉衍生物在本领域中已被公开为具有杀螨和杀虫活性，并且为天然产物合成的潜在前体。这项工作首先证明了以前在天然环糊精（CD）手性固定相（CSP）上尚未研究的异恶唑啉衍生物的手性拆分。通过不同的点击程序制备了两种基于天然CD的结构明确的CSP ，并将其用于异恶唑啉的对映体分离。发现大多数研究的异恶唑啉在反相模式下均能很好地分离（R s > 1.5），尤其是4NPh-OPr，其表现出最佳的对映选择性和分离度（α = 2.22；R s= 4.16）。通过评估流动相组成，取代部分和CSP键对分离的影响，可获得最佳分离度。这一贡献证明，在智能设计的天然CD-CSP上可以实现异恶唑啉的出色对映异构体分离，这为获得对映纯的异恶唑啉衍生物提供了一种简便而经济的方法。
• Ring-closure reactions through intramolecular substitution of thiophenoxide by oxygen and nitrogen nucleophiles: simple stereospecific synthesis of 4,5-dihydroisoxazoles and 4,5-dihydropyrazoles
  作者：Mariola Zielinska-Błajet、Rafał Kowalczyk、Jacek Skarżewski

  DOI：10.1016/j.tet.2005.03.085

  日期：2005.5

  A new and simple method for the stereospecific synthesis of 3,5-disubstituted-4,5-dihydro-isoxazoles (chiral isoxazolines) from readily available oximes of chiral Michael adducts of thiophenol to chalcones is reported. An analogous reaction with the N-arylhydrazones of the Michael adduct gave nonracemic 1-(aryl)-3,5-diphenyl-4,5-dihydro-1H-pyrazoles (chiral pyrazolines), but these products are configurationally

  报道了一种新的，简单的方法，该方法可以从苯硫酚的手性迈克尔加合物向查耳酮的易获得的肟中立体定向合成3,5-二取代的4,5-二氢-异恶唑（手性异恶唑啉）。与迈克尔加成物的N-芳基hydr类似的反应得到非外消旋的1-（芳基）-3,5-二苯基-4,5-二氢-1H-吡唑（手性吡唑啉），但是这些产物构型不稳定。合成的关键步骤是闭环反应，该反应通过噻吩氧化物的立体特异性分子内亲核取代而发生。
• Asymmetric reduction of racemic 2-isoxazolines
  作者：Masashi Tokizane、Kaori Sato、Tetsuo Ohta、Yoshihiko Ito

  DOI：10.1016/j.tetasy.2008.11.005

  日期：2008.11

  The kinetic resolution of racemic 2-isoxazolines was carried out by asymmetric reduction using borane with 1,2-amino alcohols as a chiral Source. Using excess BH3-THF in the presence of (-)-norephedrine, optically active 1,3-amino alcohol derivatives were obtained with good ee but in lower yield, while the optically active substrates 2-isoxazolines were recovered with modest ee. The asymmetric reduction using 2.0 equiv of BH3-SMe2 was investigated as an alternative strategy for the synthesis of optically active products. After reduction, treatment of the resulting Mixture with Et3N was successful in providing optically active isoxazolidine derivatives in good yields and with good ee. The choice of chiral source was also shown to have a significant effect. In particular, the use of (S)-alpha,alpha-diphenyl-2-pyrrolidinemethanol reversed the enantioselectivity of the recovered Substrates. (C) 2008 Elsevier Ltd. All rights reserved.