methyl (Z)-6,6-dimethoxyhex-3-enoate | 123331-78-2

• 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 (Z)-6,6-dimethoxyhex-3-enoate
• 英文别名: (Z)-6,6-Dimethoxy-3-hexensaeure-methylester
• CAS: 123331-78-2
• 化学式: C₉H₁₆O₄
• 分子量: 188.224
• InChiKey: LZWXGQVPIGADNL-PLNGDYQASA-N

物化性质

• 沸点：
  229.1±40.0 °C(Predicted)
• 密度：
  1.004±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (Z)-6,6-dimethoxyhex-3-enoate 在 palladium hydroxide - carbon 吡啶 、 lithium aluminium tetrahydride 、 氨 、 氢气 、 sodium 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 邻二氯苯 、 叔丁醇 为溶剂， -78.0~325.0 ℃ 、101.33 kPa 条件下， 反应 11.34h， 生成
  参考文献：
  名称：

  Further Studies on Total Synthesis of Sarain A. Efforts Toward Annulation of the Macrocyclic Rings

  摘要：

  Studies have been conducted on testing strategies for annulation of the two macrocyclic rings onto the central tricyclic nucleus of sarain A (1). In particular, methodology has been developed for introduction into the core of C-3' and C-3 substituents, which are necessary for construction of the "eastern" and "western" macrocyclic rings of I, respectively. Formation of the western ring has been successfully addressed via a ring-closing olefin metathesis strategy utilizing the Grubbs ruthenium catalyst. With this macrocyclization approach, a key intermediate lactam has been prepared which will be utilized in a total synthesis of the natural product.

  DOI：

  10.1021/jo981821d
• 作为产物：
  描述：

  1-甲氧基-1,4-环己二烯 在 高碘酸 、 间氯过氧苯甲酸 作用下， 以 甲醇 为溶剂， 反应 11.0h， 生成 methyl (Z)-6,6-dimethoxyhex-3-enoate
  参考文献：
  名称：

  受立体电子效应控制的甲硅烷基保护的五元环氧代碳鎓离子的亲核加成

  摘要：

  研究了一系列含有二硅氧烷环的稠合双环缩醛，以评估甲硅烷基保护的 2-脱氧核糖系统中的选择性来源。二硅氧烷环出人意料地使阳离子的双轴构象异构体能够通过 C-3 处的负电原子稳定。这种低能构象异构体随后经历立体电子控制的亲核加成，得到具有高非对映选择性的取代四氢呋喃。

  DOI：

  10.1021/jo400945j

文献信息

• Direct Preparation of (Z,Z)-1,4-Dienic Units with a New C6 Homologating Agent: Synthesis of α-Linolenic Acid
  作者：Jacqueline Sandri、Jacques Viala

  DOI：10.1055/s-1995-3906

  日期：1995.3

  Syntheses of two C6 homologating agents 2a and 2f are described. These agents allow direct access to the (Z,Z)-1,4-diene unit 3, a moiety present in a wide number of natural compounds. Compound 2a is prepared in 40% overall yield by selective epoxidation of methoxycyclohexa-1,4-diene followed by oxidative ring cleavage and transacetalization. Compound 2f is obtained in 90% yield by a one-step oxidative dimerization of phosphonium salt 1. A short synthetic application of these two new C6 homologating agents to the synthesis of α-linolenic acid is described.

  描述了两种C6同源试剂2a和2f的合成。这些试剂可以直接获得(Z,Z)-1,4-二烯单元3，而该单元在许多天然化合物中存在。化合物2a通过选择性环氧化甲氧基环己烯-1,4-二烯，随后进行氧化断环和转醛化，最终以40%的总收率制备而成。化合物2f通过磷盐1的一步氧化二聚反应获得，收率为90%。还描述了这两种新C6同源试剂在合成α-亚麻酸中的简短合成应用。
• Ozonolyse von Olefinen, III: S�urekatalysierte Ozonolyse von 3-Hexen-1,6-und 2-Penten-1,5-dicarbonylderivaten
  作者：Norbert Poklukar、Martin Mittelbach

  DOI：10.1007/bf00809533

  日期：——
• Mittelbach, Martin; Poklukar, Norbert; Junek, Hans, Liebigs Annalen der Chemie, 1990, # 2, p. 185 - 188
  作者：Mittelbach, Martin、Poklukar, Norbert、Junek, Hans

  DOI：——

  日期：——
• Further Studies on Total Synthesis of Sarain A. Efforts Toward Annulation of the Macrocyclic Rings
  作者：Osamu Irie、Kiyohiro Samizu、James R. Henry、Steven M. Weinreb

  DOI：10.1021/jo981821d

  日期：1999.1.1

  Studies have been conducted on testing strategies for annulation of the two macrocyclic rings onto the central tricyclic nucleus of sarain A (1). In particular, methodology has been developed for introduction into the core of C-3' and C-3 substituents, which are necessary for construction of the "eastern" and "western" macrocyclic rings of I, respectively. Formation of the western ring has been successfully addressed via a ring-closing olefin metathesis strategy utilizing the Grubbs ruthenium catalyst. With this macrocyclization approach, a key intermediate lactam has been prepared which will be utilized in a total synthesis of the natural product.
• Nucleophilic Addition to Silyl-Protected Five-Membered Ring Oxocarbenium Ions Governed by Stereoelectronic Effects
  作者：Vi Tuong Tran、K. A. Woerpel

  DOI：10.1021/jo400945j

  日期：2013.7.5

  selectivity in silyl-protected 2-deoxyribose systems. The disiloxane ring unexpectedly enables the diaxial conformer of the cation to be stabilized by an electronegative atom at C-3. This low energy conformer subsequently undergoes stereoelectronically controlled nucleophilic addition to give substituted tetrahydrofurans with high diastereoselectivity.

  研究了一系列含有二硅氧烷环的稠合双环缩醛，以评估甲硅烷基保护的 2-脱氧核糖系统中的选择性来源。二硅氧烷环出人意料地使阳离子的双轴构象异构体能够通过 C-3 处的负电原子稳定。这种低能构象异构体随后经历立体电子控制的亲核加成，得到具有高非对映选择性的取代四氢呋喃。