methyl 5-hydroxy-5-phenyl-2-pentenoate | 72853-47-5

• 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: methyl 5-hydroxy-5-phenyl-2-pentenoate
• 英文别名: methyl (E)-5-hydroxy-5-phenylpent-2-enoate
• CAS: 72853-47-5
• 化学式: C₁₂H₁₄O₃
• 分子量: 206.241
• InChiKey: VXFYGMBFRDCANQ-WEVVVXLNSA-N

物化性质

• 沸点：
  339.8±42.0 °C(Predicted)
• 密度：
  1.123±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  methyl 5-hydroxy-5-phenyl-2-pentenoate 在 palladium 10% on activated carbon 、 氢气 作用下， 以 四氢呋喃 为溶剂， 21.0 ℃ 、101.33 kPa 条件下， 反应 1.5h， 以97%的产率得到5-羟基-5-苯基戊酸甲酯
  参考文献：
  名称：

  Enzyme mediated kinetic resolution of δ-hydroxy-α,β-unsaturated esters as a route to optically active δ-lactones

  摘要：

  A novel synthetic route to optically active saturated and unsaturated delta-lactones based on enzymatic kinetic resolution and ring-closing metathesis reactions has been proposed. The influence of temperature, co-solvent, organic additives and the substrate structure on the catalytic behavior of selected hydrolases was studied. The substantial impact of the organic co-solvent and surfactant type on the enzymatic activity and enantioselectivity was observed providing enantiomerically pure delta-hydroxy-alpha,beta-unsaturated esters. The established protocol combining enzymatic kinetic resolution with ring closing metathesis was successfully applied in the synthesis of the enantiomerically pure (6R)-phenyl-5,6-dihydro-2H-pyran-2-one which plays crucial role in the synthesis of the number of bioactive compounds. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2017.05.003
• 作为产物：
  描述：

  苯甲醛 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 氯化铵 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 0.5h， 生成 methyl 5-hydroxy-5-phenyl-2-pentenoate
  参考文献：
  名称：

  通过分子内的氧杂-迈克尔反应非对映选择性合成三氟甲基化的1,3-二恶烷†

  摘要：

  描述了三氟甲基化的1，3-二恶烷的高度非对映选择性的合成。该反应以加成/氧杂-迈克尔序列进行，并且在温和的反应条件下有效地进行，具有良好的底物范围和可接受的良好收率。

  DOI：

  10.1039/c6ob02333a

文献信息

• Mixed Crossed Aldol Condensation between Conjugated Esters and Aldehydes Using Aluminum Tris(2,6-diphenylphenoxide)
  作者：Susumu Saito、Masahito Shiozawa、Hisashi Yamamoto

  DOI：10.1002/(sici)1521-3773(19990614)38:12<1769::aid-anie1769>3.0.co;2-0

  日期：1999.6.14

  The combined use of aluminum tris(2,6-diphenylphenoxide) (ATPH) and lithium 2,2,6,6-tetramethylpiperidide (LTMP) has proven to be effective for the mixed crossed aldol condensation between conjugated esters and various aldehydes. An example is shown in Equation (1).

  三（2,6-二苯基苯氧基铝）（ATPH）和2,2,6,6-四甲基哌啶锂（LTMP）的组合使用已被证明对共轭酯和各种醛之间的混合交叉羟醛缩合有效。等式（1）中示出了一个例子。
• Molecular Recognition of α,β-Unsaturated Carbonyl Compounds Using Aluminum Tris(2,6-diphenylphenoxide) (ATPH):  Structural and Conformational Analysis of ATPH Complexes and Application to the Selective Vinylogous Aldol Reaction
  作者：Susumu Saito、Takashi Nagahara、Masahito Shiozawa、Masakazu Nakadai、Hisashi Yamamoto

  DOI：10.1021/ja0205941

  日期：2003.5.1

  Various alpha,beta-unsaturated carbonyl compounds were coordinated with aluminum tris(2,6-diphenylphenoxide) (ATPH) to give the corresponding Lewis acid-base complexes in a distinctive coordination fashion (selective coordination). ATPH recognizes carbonyl substrates and subsequently orients itself as it forms a stable complex through selective coordination with the carbonyl oxygen. Selective coordination

  各种α，β-不饱和羰基化合物与铝三(2,6-二苯酚) (ATPH) 协调，以独特的配位方式（选择性配位）提供相应的路易斯酸碱配合物。ATPH 识别羰基底物，随后通过与羰基氧的选择性配位形成稳定的复合物，从而使自身定向。在ATPH的空间和电子影响下，选择性配位还赋予每个羰基化合物构象偏好，这使得α，β-不饱和羰基化合物的乙烯基醛醇反应能够产生具有不同区域和立体选择性的相应γ-醛醇产物。
• Enantioselective Syntheses of Cryptocarya Triacetate, Cryptocaryolone, and Cryptocaryolone Diacetate
  作者：Catherine M. Smith、George A. O'Doherty

  DOI：10.1021/ol0345529

  日期：2003.5.1

  products from Cryptocarya latifolia have been achieved in 13-15 steps from ethyl sorbate. The route relies upon an enantio- and regioselective Sharpless dihydroxylation and a palladium-catalyzed reduction to establish the absolute stereochemistry. The route also relies upon a highly (E)-selective olefin cross-metathesis reaction to form trans-delta-hydroxy-1-enoates. The resulting delta-hydroxy-1-enoates were

  [反应：见正文]来自山茱rypto的三种天然产物的对映选择性合成是从山梨酸乙酯经过13到15步完成的。该路线依赖于对映体和区域选择性的Sharpless二羟基化反应和钯催化的还原反应，以建立绝对的立体化学。该路线还依赖于高度（E）-选择性的烯烃交叉复分解反应以形成反式-δ-羟基-1-烯酸酯。随后将所得的δ-羟基-1-烯酸酯转化为隐乙酸三乙酸酯，隐caryolone和双隐隐caryolone。
• The Vinylogous Aldol Reaction of Unsaturated Esters and Enolizable Aldehydes Using the Novel Lewis Acid Aluminum Tris(2,6-di-2-naphthylphenoxide)
  作者：Jeffrey A. Gazaille、Tarek Sammakia

  DOI：10.1021/ol300738f

  日期：2012.6.1

  (ATNP), and its use in the vinylogous aldol reaction between methyl crotonate and enolizable aldehydes are described. ATNP is related to Yamamoto’s Lewis acid, aluminum tris(2,6-diphenylphenoxide) (ATPH), but the 2-naphthyl groups more effectively block the α-position of aldehydes, enabling the selective enolization of crotonate esters in the presence of enolizable aldehydes. Vinylogous aldol reactions

  描述了新型路易斯酸、三(2,6-二-2-萘基苯氧基铝) (ATNP) 的合成及其在巴豆酸甲酯和烯醇化醛之间的乙烯醇醛反应中的用途。ATNP 与 Yamamoto 的路易斯酸、三(2,6-二苯酚铝) (ATPH) 有关，但 2-萘基更有效地阻断醛的 α 位，从而在可烯醇化醛的存在下实现巴豆酸酯的选择性烯醇化. 然后，使用各种底物，乙烯基羟醛反应可以顺利进行并以高产率进行。
• One-pot vinylogous aldol addition of β,γ-unsaturated esters under mild conditions
  作者：İsmail Akçok、Ali Çağır

  DOI：10.1039/c5nj00961h

  日期：——

  A new methodology for the addition of β,γ-unsaturated esters to aldehydes was developed in a TMSCl, Ag₂CO₃, and TBAF mixture.

  在TMSCl，Ag2CO3和TBAF混合物中开发了一种新的方法，用于将β，γ-不饱和酯添加到醛中。