(αS)-erythro-α-methyl-3-phenyl-2-isoxazoline-5-methanol | 121523-85-1

• 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: (αS)-erythro-α-methyl-3-phenyl-2-isoxazoline-5-methanol
• 英文别名: (1S)-1-<(5R)-4,5-dihydro-3-phenyl-5-isoxazolyl>ethanol；(1S)-1-[(5R)-3-phenyl-4,5-dihydro-1,2-oxazol-5-yl]ethanol
• CAS: 121523-85-1
• 化学式: C₁₁H₁₃NO₂
• 分子量: 191.23
• InChiKey: QKHZHBZGPDGOAG-GZMMTYOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  (αS)-erythro-α-methyl-3-phenyl-2-isoxazoline-5-methanol 在 Ni-Raney 、 硼酸 氢气 作用下， 以 甲醇 、 水 为溶剂， 以100%的产率得到(3R,4S)-3,4-Dihydroxy-1-phenyl-pentan-1-one
  参考文献：
  名称：

  贝克酵母还原5-乙酰基-2-异恶唑啉的对映体纯的2,3-二羟基酮和1,2,4-三醇的合成

  摘要：

  以高收率和高对映体过量将对映选择性外消旋的5-乙酰基-2-异恶唑啉还原为5-乙醇-2-异恶唑啉。随后产生的醇的环氢解产生对映体纯的2，3-二羟基酮和1,2,4-三醇。

  DOI：

  10.1016/s0040-4039(00)82296-0
• 作为产物：
  描述：

  苯甲腈 N-氧化物 在 potassium dihydrogenphosphate 、 Diamino hydrogen phosphate 、 葡萄糖 、 baker's yeast extract 、 magnesium sulfate 作用下， 以 水 为溶剂， 反应 4.0h， 生成 (αS)-erythro-α-methyl-3-phenyl-2-isoxazoline-5-methanol
  参考文献：
  名称：

  贝克酵母还原5-乙酰基-2-异恶唑啉的对映体纯的2,3-二羟基酮和1,2,4-三醇的合成

  摘要：

  以高收率和高对映体过量将对映选择性外消旋的5-乙酰基-2-异恶唑啉还原为5-乙醇-2-异恶唑啉。随后产生的醇的环氢解产生对映体纯的2，3-二羟基酮和1,2,4-三醇。

  DOI：

  10.1016/s0040-4039(00)82296-0

文献信息

• 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。
• Diastereofacial selection in nitrile oxide cycloaddition reactions. The anti-directing effect of an allylic oxygen and some new results on the ring metalation of isoxazolines. A synthesis of (.+-.)-blastmycinone
  作者：Alan P. Kozikowski、Arun K. Ghosh

  DOI：10.1021/jo00189a024

  日期：1984.7

  the adducts to known γ-lactones. The stereochemistry associated with the metalation/alkylation of 5-alkoxymethyl-substituted isoxazolines has also been probed in order to further expand the use of these heterocycles as aldol equivalents in natural products total synthesis. A synthesis of (±)-blastmycinone (34) is reported which combines the two foregoing aspects of stereocontrol. The levels of regio-

  已经研究了与腈氧化物与带有烯丙基氧取代基的烯烃的反应有关的非对映选择性的程度。当3-丁烯-2-醇（5）或（+）-（S）-异亚丙基-3-丁烯-1,2-二醇（1）的叔丁基二甲基甲硅烷基醚衍生物为1时，已发现合理的非对映选择性水平。用作双极亲虫。这些环加成反应的立体化学过程已通过将加合物转化为已知的γ-内酯的方法得到严格证明。还探索了与5-烷氧基甲基取代的异恶唑啉的金属化/烷基化有关的立体化学，以进一步扩展这些杂环作为天然产物总合成中的羟醛等效物的用途。据报道，（±）-blastcincinone（34）的合成结合了立体声控制的上述两个方面。还讨论了在由异亚丙基-D-甘油醛制得的顺式和反式二取代的烯烃35和39的环加成反应中发现的区域选择性和立体选择性。给出了手性烯烃与手性腈的反应的单个例子。
• Stereoselective nitrile oxide cycloadditions to chiral allyl ethers and alcohols. The inside alkoxy effect
  作者：K. N. Houk、Susan R. Moses、Yun Dong Wu、Nelson G. Rondan、Volker Jager、R. Schohe、Frank R. Fronczek

  DOI：10.1021/ja00325a040

  日期：1984.6
• 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.
• 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.