(Z)-3-(3,4-dimethoxyphenyl)-3-(5-formyl-2-methoxyphenoxy)acrylic acid methyl ester | 868258-14-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (Z)-3-(3,4-dimethoxyphenyl)-3-(5-formyl-2-methoxyphenoxy)acrylic acid methyl ester
• 英文别名: methyl (Z)-3-(3,4-dimethoxyphenyl)-3-(5-formyl-2-methoxyphenoxy)prop-2-enoate
• CAS: 868258-14-4
• 化学式: C₂₀H₂₀O₇
• 分子量: 372.375
• InChiKey: RLWNEOSYZGAVIK-BOPFTXTBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (Z)-3-(3,4-dimethoxyphenyl)-3-(5-formyl-2-methoxyphenoxy)acrylic acid methyl ester 在 哌啶 、 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 1-di(2-(5-methylfuryl)phosphanyl)ferrocene 、 [RhCl(coe)2]2 、 4 A molecular sieve 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 氯仿 、 甲苯 、 苯 为溶剂， 反应 99.33h， 生成 2-(3,4-dimethoxyphenyl)-4-{2-[2-(3,4-dimethoxyphenyl)-1-methoxycarbonylethoxycarbony]vinyl}-7-methoxy-2,3-dihydrobenzofuran-3-carboxylic acid methyl ester
  参考文献：
  名称：

  Total Synthesis of (+)-Lithospermic Acid by Asymmetric Intramolecular Alkylation via Catalytic C−H Bond Activation

  摘要：

  The total synthesis of (+)-lithospermic acid is described. The efficient synthesis features an asymmetric alkylation via C-H bond activation to assemble the dihydrobenzofuran core of the natural product. This was accomplished via a chiral imine-directed C-H bond functionalization and represents the first application of this C-H activation method to natural product synthesis. Furthermore, a challenging deprotection of a late-stage permethylated lithospermic acid was achieved.

  DOI：

  10.1021/ja052680h
• 作为产物：
  描述：

  2,2-dibromo-1-(3,4-dimethoxyphenyl)ethene 在 正丁基锂 、 sodium methylate 作用下， 以 甲醇 、 正己烷 为溶剂， 反应 4.5h， 生成 (Z)-3-(3,4-dimethoxyphenyl)-3-(5-formyl-2-methoxyphenoxy)acrylic acid methyl ester
  参考文献：
  名称：

  Total Synthesis of (+)-Lithospermic Acid by Asymmetric Intramolecular Alkylation via Catalytic C−H Bond Activation

  摘要：

  The total synthesis of (+)-lithospermic acid is described. The efficient synthesis features an asymmetric alkylation via C-H bond activation to assemble the dihydrobenzofuran core of the natural product. This was accomplished via a chiral imine-directed C-H bond functionalization and represents the first application of this C-H activation method to natural product synthesis. Furthermore, a challenging deprotection of a late-stage permethylated lithospermic acid was achieved.

  DOI：

  10.1021/ja052680h

文献信息

• Asymmetric Intramolecular Alkylation of Chiral Aromatic Imines via Catalytic C-H Bond Activation
  作者：Robert Bergman、Jonathan Ellman、Anja Watzke、Rebecca Wilson、Steven O’Malley

  DOI：10.1055/s-2007-985593

  日期：2007.9

  substitution patterns using chiral phosphor- amidite ligands. However, for other alkene substitution patterns, alternative approaches for achieving asymmetric induction may be necessary. In the context of the first total synthesis of (+)-lithospermic acid, the first example of employing a chiral imine as a directing group in catalytic C - H bond activation was developed. Specifically, imine 2, prepared by condensation

  通过催化 C-H 键活化手性芳族亚胺的不对称分子内烷基化 Anja Watzke, Rebecca M。威尔逊、史蒂文 J. 奥马利、罗伯特 G. 伯格曼、* 乔纳森 A . Ellman* 加州大学伯克利分校劳伦斯伯克利国家实验室化学系和化学科学部，CA 94720，美国传真 [phone]；电子邮箱：[e-mail]；电子邮件：[e-mail] 2007 年 4 月 16 日收到 摘要：研究了手性芳香醛亚胺的不对称分子内烷基化，其中差异取代的烯烃与亚胺间位连接。由氨基茚满衍生物制备的亚胺获得了高对映选择性，其作为铑催化的 C-H 键活化的导向基团。通过使用空间位阻非手性亚胺底物和催化量的手性胺，也实现了催化不对称分子内烷基化的初步证明。在之前发表的工作中，我们评估了一系列结构多样的手性胺导向基团，其中氨基茚满被证明是最有效
• Total Synthesis of (+)-Lithospermic Acid by Asymmetric Intramolecular Alkylation via Catalytic C−H Bond Activation
  作者：Steven J. O'Malley、Kian L. Tan、Anja Watzke、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/ja052680h

  日期：2005.10.1

  The total synthesis of (+)-lithospermic acid is described. The efficient synthesis features an asymmetric alkylation via C-H bond activation to assemble the dihydrobenzofuran core of the natural product. This was accomplished via a chiral imine-directed C-H bond functionalization and represents the first application of this C-H activation method to natural product synthesis. Furthermore, a challenging deprotection of a late-stage permethylated lithospermic acid was achieved.