trans-methyl 3-(4-fluorophenyl)oxirane-2-carboxylate

• 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: trans-methyl 3-(4-fluorophenyl)oxirane-2-carboxylate
• 英文别名: ethyl (2S,3R)-3-(4-fluorophenyl)oxirane-2-carboxylate
• 化学式: C₁₁H₁₁FO₃
• 分子量: 210.205
• InChiKey: LOQUCVJPGYTPKB-ZJUUUORDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-methyl 3-(4-fluorophenyl)oxirane-2-carboxylate 在 sodium azide 、 氯化铵 作用下， 以 乙醇 为溶剂， 反应 8.0h， 生成 (2S,3S)-2-Azido-3-(4-fluoro-phenyl)-3-hydroxy-propionic acid ethyl ester
  参考文献：
  名称：

  基于应变的炔丙基胺的多功能合成平台

  摘要：

  不同的反应性：各种乙炔基氮丙啶表现为应变的炔丙基胺，可通过高度非对映选择性的S N 2'氢化物传输直接转化为未保护的α-氨基丙二烯（参见方案）。其他反应途径包括化学和区域选择性转化为双环氮丙啶/烯醇醚或高度紧张的叠氮炔。

  DOI：

  10.1002/anie.200906066
• 作为产物：
  描述：

  ethyl 4-fluorocinnamate 在 dibromamine-T 、 水 、 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 0.84h， 以73%的产率得到trans-methyl 3-(4-fluorophenyl)oxirane-2-carboxylate
  参考文献：
  名称：

  Efficient Protocol for Stereoselective Epoxidation of Cinnamic Esters Using TsNBr₂

  摘要：

  An efficient method has been developed for the synthesis of epoxide from cinnamic esters without any catalyst. The reaction was performed in CH(3)CN-water (4/1) using N,N-dibromo-p-toluenesulfonamide (TsNBr(2)) in alkaline conditions. This procedure can be utilized for stereoselective synthesis of epoxides from cinnamic esters in excellent yield in a shorter reaction time with exclusive formation of the trans-isomer. The method was further extended successfully for styrenes.

  DOI：

  10.1080/00397910903318617

文献信息

• Highly Efficient Asymmetric Epoxidation of Electron-Deficient α,β-Enones and Related Applications to Organic Synthesis
  作者：Changwu Zheng、Yawen Li、Yingquan Yang、Haifeng Wang、Haifeng Cui、Junkang Zhang、Gang Zhao

  DOI：10.1002/adsc.200900041

  日期：2009.7

  The asymmetric epoxidation of electron‐deficient olefins has been achieved using inexpensive and readily available prolinols as catalysts with good to excellent yields and enantioselectivities. The utility of the resulting chiral epoxides was illustrated by elaboration to several synthetically useful compounds featuring a concise synthesis of (−)‐(5R,6S)‐balasubramide.

  使用价格低廉，易于获得的脯氨醇作为催化剂，可以实现电子不足的烯烃的不对称环氧化，其收率和对映选择性都非常好。详细阐述了几种合成有用的化合物，这些化合物以（-）-（5 R，6 S）-巴拉苏酰胺的简明合成为例，说明了所得手性环氧化物的实用性。
• Metal-free ring-opening of epoxides with potassium trifluoroborates
  作者：Silvia Roscales、Aurelio G. Csákÿ

  DOI：10.1039/c3cc47360k

  日期：——

  The ring-opening of epoxides with potassium trifluoroborates proceeds smoothly in the presence of trifluoroacetic anhydride under metal-free conditions. The reactions are regioselective and afford a single diastereomer. Both electron-rich and electron-poor aryltrifluoroborates are tolerated.

  在三氟乙酸酐存在下，环氧化物与三氟硼酸钾的开环反应在无金属条件下顺利进行。反应具有区域选择性，并产生单一非对映异构体。富电子和贫电子芳基三氟硼酸盐均可被容忍。
• Highly Enantioselective Epoxidation of α,β-Unsaturated Esters by Chiral Dioxirane
  作者：Xin-Yan Wu、Xuegong She、Yian Shi

  DOI：10.1021/ja020478y

  日期：2002.7.1

  This paper describes a highly enantioselective epoxidation of α,β-unsaturated esters using the fructose-derived ketone 2 as catalyst and Oxone as oxidant. High ee's have been obtained for a number of trans and trisubstituted substrates (82−98% ee). The results described show that it is feasible for dioxiranes to effectively epoxidize electron-deficient olefins with high ee's.

  本文描述了使用果糖衍生的酮 2 作为催化剂和 Oxone 作为氧化剂的 α,β-不饱和酯的高度对映选择性环氧化。许多反式和三取代底物 (82-98% ee) 都获得了高 ee。所描述的结果表明，二环氧乙烷有效地环氧化具有高ee值的缺电子烯烃是可行的。
• Design and characterization of mechanism-based inhibitors for the tyrosine aminomutase SgTAM
  作者：Timothy J. Montavon、Carl V. Christianson、Grace M. Festin、Ben Shen、Steven D. Bruner

  DOI：10.1016/j.bmcl.2007.11.046

  日期：2008.5

  The synthesis and evaluation of two classes of inhibitors for SgTAM, a 4-methylideneimidazole-5-one (MIO) containing tyrosine aminomutase, are described. A mechanism-based strategy was used to design analogs that mimic the substrate or product of the reaction and form covalent interactions with the enzyme through the MIO prosthetic group. The analogs were characterized by measuring inhibition constants and X-ray crystallographic structural analysis of the co-complexes bound to the aminomutase, SgTAM.
• A Versatile Synthetic Platform Based on Strained Propargyl Amines
  作者：Zhi He、Andrei K. Yudin

  DOI：10.1002/anie.200906066

  日期：2010.2.22

  Divergent reactivity: Various ethynylaziridines behave as strained propargyl amines and can be directly converted into unprotected α‐amino allenes by a highly diastereoselective SN2′ hydride delivery (see scheme). Additional reaction routes involve chemo‐ and regioselective transformation into either bicyclic aziridine/enol ethers or highly strained azirine alkynes.

  不同的反应性：各种乙炔基氮丙啶表现为应变的炔丙基胺，可通过高度非对映选择性的S N 2'氢化物传输直接转化为未保护的α-氨基丙二烯（参见方案）。其他反应途径包括化学和区域选择性转化为双环氮丙啶/烯醇醚或高度紧张的叠氮炔。