(4S,2E)-ethyl 4-hydroxy-2-methylpent-2-enoate | 114191-19-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (4S,2E)-ethyl 4-hydroxy-2-methylpent-2-enoate
• 英文别名: (S,E)-ethyl 4-hydroxy-2-methylpent-2-enoate；ethyl (E,4S)-4-hydroxy-2-methylpent-2-enoate
• CAS: 114191-19-4
• 化学式: C₈H₁₄O₃
• 分子量: 158.197
• InChiKey: MEPMTWFXIVYSOK-XPPMVYLVSA-N

物化性质

• 沸点：
  242.0±23.0 °C(predicted)
• 密度：
  1.018±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4S,2E)-ethyl 4-hydroxy-2-methylpent-2-enoate 在 sodium hydride 作用下， 生成 O-(2R,3E)-4-Ethoxycarbonylpent-3-en-2-yl S-methyldithiocarbonate
  参考文献：
  名称：

  使用手性转移通过黄原酸烯丙酯至二硫代碳酸酯的重排进行硫代反酸的不对称合成。（5 R）-2,5-二氢-4-羟基-5-甲基-3-苯基-5-丙-1'-烯基-2-氧代噻吩的X射线晶体结构

  摘要：

  已经开发了基于黄原酸烯丙基酯至二硫代碳酸酯重排的硫代反酸的不对称合成，通过X射线晶体结构测定证实了产物的绝对构型。

  DOI：

  10.1039/c39870001228
• 作为产物：
  描述：

  (S)-2-((tert-butyldimethylsilyl)oxy)propan-1-ol 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以88%的产率得到(4S,2E)-ethyl 4-hydroxy-2-methylpent-2-enoate
  参考文献：
  名称：

  Chambers, Mark S.; Thomas, Eric J., Journal of the Chemical Society. Perkin transactions I, 1997, # 4, p. 417 - 431

  摘要：

  DOI：

文献信息

• Synthesis of Optically Active β,γ-Unsaturated α-Amino Acids and of α,β-Unsaturated γ-Amino Acids. SN2- vs. SN2’-Dichotomy of the Mitsunobu Amination of Allylic Alcohols
  作者：Johann Mulzer、Günther Funk

  DOI：10.1055/s-1995-3847

  日期：1995.1

  Novel and efficient syntheses (6-9 steps, overall yields 10-30%) are described for optically pure β,γ-unsaturated α-amino acids and α,β-unsaturated γ-amino acids, starting from (R)-isopropylidene glyceraldehyde and ethyl (S)-lactate, respectively. The key step is the Mitsunobu reaction of chiral secondary allylic alcohols with phthalimide as the nucleophile, where α,γ allylic transpositions are observed for the first time. The structure-α,γ-ratio-relationship is studied and also the stereochemistry of the allylic transposition. The α-substitution proceeds via clean SN2 inversion, whereas the γ-substitution corresponds to an (E)-anti attack of the nucleophilic with varying stereoselectivities.

  本文描述了从（R）-异丙叉甘油醛和乙基（S）-乳酸分别合成光学纯的β,γ-不饱和α-氨基酸和α,β-不饱和γ-氨基酸的新颖且高效的方法（总步骤为6-9步，总收率为10-30%）。关键步骤是手性仲烯丙醇与酞酰亚胺作为亲核试剂的 Mitsunobu 反应，首次观察到α,γ 烯丙基重排现象。研究了结构-α,γ 比例关系以及烯丙基重排的立体化学。α-取代过程通过干净的 SN2 反转进行，而γ-取代对应于亲核试剂的（E）-反向攻击，具有不同的立体选择性。
• Catalytic osmylation of electron poor allylic alcohols and ethers.
  作者：Anna Bernardi、Silvia Cardani、Carlo Scolastico、Roberto Villa.

  DOI：10.1016/s0040-4020(01)85840-3

  日期：1988.1

  The catalytic osmylation of electron-poor allylic ethers and alcohols was studied. In the case of γ-alkoxy E-enoates reaction selectivity was found to range from 2:1 to 8:1 in favor of the arabino (2,3-syn - 3,4-anti) product, regardless of the double bond substitution. Lower (if any) selectivity was found for the Z-isomers. On the contrary, 2-Mthylene-3-hydroxy esters were osmylated with virtually

  研究了贫电子烯丙基醚和醇的催化渗透作用。在γ-烷氧基E-烯酸酯的情况下，发现反应选择性在2：1至8：1的范围内，有利于阿拉伯糖（2,3-syn-3,4-anti）产物，无论双键取代如何。发现Z异构体的选择性较低（如果有的话）。相反，2-甲亚甲基-3-羟基酯几乎完全被2,3-syn选择性地进行了甲磺酰化反应。讨论了影响反应的立体化学结果的因素
• The nucleophilic addition of α-metallated 1,3-dioxanes to planar chiral cationic η³-allylmolybdenum complexes. Synthesis of (2E,5S,6R,7E)-6-methyl-8-phenylocta-2,7-dienoic acid methyl ester, a key component of the Cryptophycins
  作者：John Cooksey、Andrew Gunn、Philip J. Kocienski、Alexander Kuhl、Sukhjinder Uppal、John A. Christopher、Richard Bell

  DOI：10.1039/b400242c

  日期：——

  addition of a 1,3-dioxan-4-ylcopper(I) reagent to a cationic eta3-allylmolybdenum complex as part of a synthesis of (2E,5S,6R,7E)-6-methyl-8-phenylocta-2,7-dienoic acid, a key component of the Cryptophycins. Oxidative addition of Mo(CO)(4)(THF)(2) to allyl benzoates provides an efficient synthesis of eta3-allylmolybdenum(dicarbonyl) complexes.

  通过将1，3-二恶烷-4-基铜（I）试剂亲核加成到阳离子eta3-烯丙基钼络合物中，作为（2E，5S，6R，7E）合成的一部分，构建了两个相邻的立体异构中心和一个侧链烯烃。 -6-甲基-8-苯基辛基-2,7-二烯酸，隐藻霉素的关键成分。Mo（CO）（4）（THF）（2）氧化加成到苯甲酸烯丙酯中，可有效合成eta3-烯丙基钼（二羰基）配合物。
• Highly enantioselective sequential Claisen–Ireland/metathesis: synthesis of cycloalkenes bearing two contiguous highly functionalized asymmetric centres
  作者：Antoine Français、Olivier Bedel、Willy Picoul、Abdelkrim Meddour、Jacques Courtieu、Arnaud Haudrechy

  DOI：10.1016/j.tetasy.2004.12.029

  日期：2005.3

  A sequence of two reactions, consisting of a highly stereoselective silylated ketene acetal Claisen-Ireland rearrangement followed by a ring closing metathesis, gave a stereocontrolled access to various carbocycles. (C) 2005 Published by Elsevier Ltd.
• Highly Stereoselective Epoxidation of α-Methyl-γ-hydroxy-α,β-unsaturated Esters:  Rationalization and Synthetic Applications
  作者：Irakusne López、Santiago Rodríguez、Javier Izquierdo、Florenci V. González

  DOI：10.1021/jo0709955

  日期：2007.8.1

  The diastereoselectivity of the nucleophilic epoxidation of gamma-hydroxy-alpha, beta-unsaturated esters having a methyl substituent at the alpha- or beta-position was investigated. Epoxidation of the alpha-methyl-substituted enoate was highly stereoselective, giving rise to the syn isomer. This finding was used to perform an enantioselective synthesis of a natural product having a beta-hydroxy-alpha-methylene-gamma-butyrolactone motif. The nucleophilic epoxidation of enoates was found to be irreversible. Models to explain the observed stereoselectivities are proposed.