(2R,3S)-trans-(4-methoxyphenyl)glycidic acid ethyl ester | 106044-85-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (2R,3S)-trans-(4-methoxyphenyl)glycidic acid ethyl ester
• 英文别名: ethyl (2R,3S)-3-(4-methoxyphenyl)oxirane-2-carboxylate；ethyl (2R,3S)-3-(4-methoxyphenyl)glycidate
• CAS: 106044-85-3
• 化学式: C₁₂H₁₄O₄
• 分子量: 222.241
• InChiKey: VLSGACWGKWLNCR-WDEREUQCSA-N

物化性质

• 沸点：
  313.0±42.0 °C(Predicted)
• 密度：
  1.191±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  48.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  对甲氧基肉桂酸乙酯 在 叔丁基过氧化氢 、 4 A molecular sieve yttrium(III) isopropoxide 、 (S)-6,6'-[oxybis(ethylene)dioxy]biphenyl-2,2'-diol 、 三苯胂氧化物 作用下， 以 四氢呋喃 为溶剂， 反应 45.0h， 以74%的产率得到(2R,3S)-trans-(4-methoxyphenyl)glycidic acid ethyl ester
  参考文献：
  名称：

  使用钇-联苯二醇配合物催化 α,β-不饱和酯的不对称环氧化

  摘要：

  我们使用 2-10 mol% 的钇-手性联苯二醇催化剂通过氧化剂的共轭加成成功地进行了 α,β-不饱和酯的催化不对称环氧化反应。多种具有 β-芳基和 β-烷基取代基的底物被有效环氧化，产生相应的 α,β-环氧酯，产率高达 97%，ee 高达 99%。

  DOI：

  10.1021/ja052466t

文献信息

• 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。
• A Catalytic Asymmetric Synthesis of Chiral Glycidic Acid Derivatives through Chiral Dioxirane-Mediated Catalytic Asymmetric Epoxidation of Cinnamic Acid Derivatives
  作者：Ritsuo Imashiro、Masahiko Seki

  DOI：10.1021/jo049893u

  日期：2004.6.1

  A novel and practical asymmetric synthesis of chiral glycidic acid derivatives involving methyl (2R,3S)-3-(4-methoxyphenyl)glycidate ((2R,3S)-2a), a key intermediate for diltiazem hydrochloride (1), was developed. Treatment of methyl (E)-4-methoxycinnamate ((E)-3a) with chiral dioxirane, generated in situ from a catalytic amount (5 mol %) of an 11-membered C2-symmetric binaphthyl ketone (R)-7a, provided

  一种新颖实用的不对称合成手性缩水甘油酸衍生物，涉及（2 R，3 S）-3-（4-甲氧基苯基）缩水甘油酸甲酯（（2 R，3 S）-2a），这是盐酸地尔硫卓的关键中间体（1） ， 发展了。甲基的处理（ë）-4-甲氧基肉桂酸酯（（ë - ）3a中的11元的）与手性双环氧乙烷，从催化量原位产生（5摩尔％）c ^ 2 -对称联萘酮（[R ）-图7a，提供（2 R，3 S）-2a产率为92％，ee为80％。通过使用相同的方法，将其他肉桂酸酯和酰胺环氧化，得到相应的手性缩水甘油酸衍生物，产率高达95％，ee为92％。观察到（E）-肉桂酸酯不对称环氧化的对映选择性比（E）-二苯乙烯衍生物更高的对映选择性，并被认为归因于肉桂酸酯中的酯基团的氧原子与内酯的氧原子之间的偶极-偶极排斥。联萘基二环氧乙烷中的部分。
• Facile synthesis of (2R,3S)-3-(4-Methoxyphenyl)glycidic esters via optical resolution of the unisolated labile free acid
  作者：Masao Yamamoto、Masatoshi Hayashi、Mitsuo Masaki、Hiroyuki Nohira

  DOI：10.1016/s0957-4166(00)82162-x

  日期：1991.1

  (2R,3S)-3-(4-Methoxyphenyl)glycidic esters were efficiently synthesized by the optical resolution of the racemic acid and esterification of the optically active acid thus obtained, in the form of its alkali metal salt.

  通过外消旋酸的旋光拆分和由此获得的旋光酸的碱金属盐形式的酯化反应，可以有效地合成（2 R，3 S）-3-（4-甲氧基苯基）缩水甘油酯。
• Chemoenzymatic approach to optically active phenylglycidates: resolution of bromo- and iodohydrins
  作者：Naveen Anand、Munish Kapoor、Surrinder Koul、Subhash C. Taneja、Rattan L. Sharma、Ghulam N. Qazi

  DOI：10.1016/j.tetasy.2004.08.026

  日期：2004.10

  Enantiomerically enriched phenylglycidates, precursors of the taxol C-13 phenylisoserine side chain and diltiazem. were prepared by kinetic resolution of anti-2-bromo-3-hydroxy- and anti-3-hydroxy-2-iodophenylpropanoates to provide enantioriched (2R,3R)- and (2S,3S)-halohydrins. The bulkiness and inflexibility of bromo and iodo groups in halohydrins have made them inaccessible to the active site of most of the lipases utilized for the hydrolysis of their acyloxy derivatives. In a set of 22 hydrolases screened herein, including native as well as commercial enzymes, only Aspergillus niger (Lipase AS, AMANO) could catalyze the hydrolysis with high enantioselectivity (E = 176). The resolved halohydrins easily underwent transformation to the corresponding (2S,3R)- and (2R,3S)phenylglycidates. (C) 26 E'lsevier Ltd. All rights reserved.
• 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.