(5RS)-5-<(1SR)-1-hydroxypropyl>-3-phenyl-2-isoxazoline | 138587-66-3

• 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: (5RS)-5-<(1SR)-1-hydroxypropyl>-3-phenyl-2-isoxazoline
• 英文别名: anti-5-(1-hydroxypropyl)-3-phenyl-4,5-dihydroisoxazole；(1S)-1-[(5R)-3-phenyl-4,5-dihydro-1,2-oxazol-5-yl]propan-1-ol
• CAS: 138587-66-3；138587-76-5；138622-09-0；138622-10-3
• 化学式: C₁₂H₁₅NO₂
• 分子量: 205.257
• InChiKey: BFFRMKGDXONMOO-NWDGAFQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  3
• 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

• 作为反应物：
  描述：

  (5RS)-5-<(1SR)-1-hydroxypropyl>-3-phenyl-2-isoxazoline 在 氢气 、 硼酸 、 镍 作用下， 以 甲醇 、 水 为溶剂， 反应 2.0h， 以62%的产率得到syn-3,4-dihydroxy-1-phenylhexan-1-one
  参考文献：
  名称：

  Nucleophilic additions to and reductiosn of 5-formyl-and 5-acyl-2-isoxazolines (4,5-dihydeoisoxazoles): a stereoselective route to β,γ-dihydroxy ketones

  摘要：

  Reductions of readily available 5-acyl-2-isoxazolines with L-Selectride follow the Felkin-Anh model and produce syn-5-hydroxyalkyl-2-isoxazolines with excellent (> 95:5) selectivities. Swern oxidation of 5-hydroxymethyl-2-isoxazolines, followed by direct addition of a Grignard reagent to the intermediate 5-formyl-2-isoxazolines, also follows the Felkin-Anh model and produces anti-5-hydroxyalkyl-2-isoxazolines with modest (80:20) to excellent (> 95:5) selectivity. In contrast, additions of Grignard reagents to 5-acyl-2-isoxazolines follow the chelation model, and give syn or anti products (depending on choice of acyl substituent and Grignard reagent) with good (90:10) to excellent selectivity. These selectivities are almost always far superior to those that can be obtained by direct nitrile oxide cycloaddition to a chiral allylic alcohol or ether. The resulting products are readily reduced to syn- or anti-beta,gamma-dihydroxy ketones. A speculative model to explain this surprising reversal in selectivity between formyl and acyl isoxazolines is proposed.

  DOI：

  10.1039/p19910002613
• 作为产物：
  描述：

  benzohydroximoyl chloride 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 96.0h， 生成 (5RS)-5-<(1SR)-1-hydroxypropyl>-3-phenyl-2-isoxazoline
  参考文献：
  名称：

  通过羟肟基氯的O-金属化生成腈氧化物。氮氧化物与α-取代的烯丙醇的螯合控制的顺-选择性环加成反应

  摘要：

  据报道，通过用有机金属化合物处理羟肟基氯，新一代的腈氧化物。它们在1-位手性中心的烯丙醇上的环加成是以顺选择性方式进行的，这是借助金属螯合来立体控制1,3-偶极环加成的第一个例子。

  DOI：

  10.1016/0040-4039(91)80171-2

文献信息

• 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.
• Generation of nitrile oxides through O-metalation of hydroximoyl chlorides. Chelation-controlled syn-selective cycloaddition of nitrile oxides to α-substituted allyl alcohols
  作者：Shuji Kanemasa、Shigeru Kobayashi、Shigeru Kobayashi、Masaki Nishiuchi、Hidetoshi Yamamoto、Eiji Wada

  DOI：10.1016/0040-4039(91)80171-2

  日期：1991.10

  New generation of nitrile oxides by treatment of hydroximoyl chlorides with organometallics is reported. Their cycloadditions to the allyl alcohols bearing a chiral center at the 1-position proceed in a syn-selective manner, providing the first example of stereocontrol of 1,3-dipolar cycloaddition by the aid of metal chelation.

  据报道，通过用有机金属化合物处理羟肟基氯，新一代的腈氧化物。它们在1-位手性中心的烯丙醇上的环加成是以顺选择性方式进行的，这是借助金属螯合来立体控制1,3-偶极环加成的第一个例子。
• Nucleophilic additions to and reductiosn of 5-formyl-and 5-acyl-2-isoxazolines (4,5-dihydeoisoxazoles): a stereoselective route to β,γ-dihydroxy ketones
  作者：Dennis P. Curran、Jaincun Zhang

  DOI：10.1039/p19910002613

  日期：——

  Reductions of readily available 5-acyl-2-isoxazolines with L-Selectride follow the Felkin-Anh model and produce syn-5-hydroxyalkyl-2-isoxazolines with excellent (> 95:5) selectivities. Swern oxidation of 5-hydroxymethyl-2-isoxazolines, followed by direct addition of a Grignard reagent to the intermediate 5-formyl-2-isoxazolines, also follows the Felkin-Anh model and produces anti-5-hydroxyalkyl-2-isoxazolines with modest (80:20) to excellent (> 95:5) selectivity. In contrast, additions of Grignard reagents to 5-acyl-2-isoxazolines follow the chelation model, and give syn or anti products (depending on choice of acyl substituent and Grignard reagent) with good (90:10) to excellent selectivity. These selectivities are almost always far superior to those that can be obtained by direct nitrile oxide cycloaddition to a chiral allylic alcohol or ether. The resulting products are readily reduced to syn- or anti-beta,gamma-dihydroxy ketones. A speculative model to explain this surprising reversal in selectivity between formyl and acyl isoxazolines is proposed.