methyl (2E,6E)-5-hydroxy-7-phenylhepta-2,6-dienoate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: methyl (2E,6E)-5-hydroxy-7-phenylhepta-2,6-dienoate
• 英文别名: (2E,6E)-methyl-5-hydroxy-7-phenylhepta-2,6-dienoate
• 化学式: C₁₄H₁₆O₃
• 分子量: 232.279
• InChiKey: VUILPHNRZJUSCY-NJNCEADSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.21
• 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 (2E,6E)-5-hydroxy-7-phenylhepta-2,6-dienoate 、 乙腈 在 CoCl₂ 乙酸酐 作用下， 反应 20.0h， 以26%的产率得到(2E,6E)-5-Acetoxy-7-phenyl-hepta-2,6-dienoic acid methyl ester
  参考文献：
  名称：

  Cobalt(II)-Catalyzed Conversion of Allylic Alcohols/Acetates to Allylic Amides in the Presence of Nitriles

  摘要：

  Various secondary allylic alcohols or their acetates and tertiary allylic alcohols can be converted to the corresponding transposed allylic amides in the presence of a catalytic quantity of cobalt(II) chloride and acetic anhydride in acetonitrile. Tertiary alcohols undergo complete rearrangement whereas secondary ones afford a mixture of regioisomers. Moderate yields of amides are also obtained by reacting acrylonitrile with secondary alcohols in 1,2-dichloroethane. The presence of acetic anhydride or acetic acid is crucial to the formation of amides as the absence of the former affords no amides and the allylic alcohols are mainly recovered as regioisomeric mixtures. The regioselectivity during amide formation can be enhanced by using cobalt complexes 14-16 in acetic acid medium. Some preliminary studies indicate that these reactions are proceeding via an pi-allyl complex or tight ion pair rather than a [3,3] sigmatropic rearrangement of acetamidate obtained in a Pinner reaction.

  DOI：

  10.1021/jo00114a013
• 作为产物：
  描述：

  巴豆酸甲酯 、 肉桂醛 在 aluminum tris(2,6-diphenylphenoxide) 、 2,2,6,6-tetramethylpiperidinyl-lithium 作用下， 以 甲苯 、 四氢呋喃 、 正己烷 为溶剂， 反应 0.83h， 以71%的产率得到methyl (2E,6E)-5-hydroxy-7-phenylhepta-2,6-dienoate
  参考文献：
  名称：

  使用三（2,6-二苯酚铝）铝在共轭酯和醛之间的混合交叉羟醛缩合反应

  摘要：

  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。

  DOI：

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

文献信息

• 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。
• FUJITA TSUTOMU; WATANABE SHOJI; SUGA KYOICHI; NAGASE TOMOYASU, ISR. J. CHEM. <ISJC-AT>, 1974, 12, NO 5, 971-976
  作者：FUJITA TSUTOMU、 WATANABE SHOJI、 SUGA KYOICHI、 NAGASE TOMOYASU

  DOI：——

  日期：——
• 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。
• Cobalt(II)-Catalyzed Conversion of Allylic Alcohols/Acetates to Allylic Amides in the Presence of Nitriles
  作者：Manoj Mukhopadhyay、M. Madhava Reddy、G. C. Maikap、Javed Iqbal

  DOI：10.1021/jo00114a013

  日期：1995.5

  Various secondary allylic alcohols or their acetates and tertiary allylic alcohols can be converted to the corresponding transposed allylic amides in the presence of a catalytic quantity of cobalt(II) chloride and acetic anhydride in acetonitrile. Tertiary alcohols undergo complete rearrangement whereas secondary ones afford a mixture of regioisomers. Moderate yields of amides are also obtained by reacting acrylonitrile with secondary alcohols in 1,2-dichloroethane. The presence of acetic anhydride or acetic acid is crucial to the formation of amides as the absence of the former affords no amides and the allylic alcohols are mainly recovered as regioisomeric mixtures. The regioselectivity during amide formation can be enhanced by using cobalt complexes 14-16 in acetic acid medium. Some preliminary studies indicate that these reactions are proceeding via an pi-allyl complex or tight ion pair rather than a [3,3] sigmatropic rearrangement of acetamidate obtained in a Pinner reaction.