methyl 3-hydroxy-5-methyl-2-methylene-4-hexenoate | 148901-34-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: methyl 3-hydroxy-5-methyl-2-methylene-4-hexenoate
• 英文别名: Methyl 3-hydroxy-5-methyl-2-methylidenehex-4-enoate
• CAS: 148901-34-2
• 化学式: C₉H₁₄O₃
• 分子量: 170.208
• InChiKey: HAEBCMMGLWEXEN-UHFFFAOYSA-N

物化性质

• 沸点：
  258.9±40.0 °C(predicted)
• 密度：
  1.020±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.44
• 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 3-hydroxy-5-methyl-2-methylene-4-hexenoate 在 三乙胺 作用下， 以 乙醚 为溶剂， 反应 3.5h， 生成 diethyl (2Z)-2-methoxycarbonyl-5-methyl-2,4-hexadienylphosphonate
  参考文献：
  名称：

  A Novel Route to Substituted Trienes and Tetraenes

  摘要：

  The reaction sequence involving Arbuzov rearrangement of allyl phosphites 4 to phosphonates 5 followed by Horner-Wadsworth-Emmons olefination of 5 with aldehydes gives substituted trienes and tetraenes 8 with full stereoselectivity.

  DOI：

  10.1080/00397919308009822
• 作为产物：
  描述：

  3-甲基-2-丁烯醛 、 丙烯酸甲酯（MA） 在 三乙烯二胺 、 1-n-butyl-2,3-dimethylimidazolium hexafluorophosphate 作用下， 反应 24.0h， 以19%的产率得到methyl 3-hydroxy-5-methyl-2-methylene-4-hexenoate
  参考文献：
  名称：

  Baylis–Hillman reaction in [bdmim][PF 6 ] ionic liquid

  摘要：

  A new use of ionic liquid [bdmim][PF6] as solvent for the Baylis-Hillman reaction is presented. Unlike the commonly used [bmim][PF6] that evidently reacts with electrophilic aldehydes under basic conditions, ionic liquid [bdmim][PF6] is inert and the Baylis-Hillman reaction in [bdmim][PF6] proceeds smoothly with better yield. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.04.099

文献信息

• Terminating catalytic asymmetric Heck cyclizations by stereoselective intramolecular capture of η3-allylpalladium intermediates: total synthesis of (−)-spirotryprostatin B and three stereoisomers
  作者：Larry E. Overman、Mark D. Rosen

  DOI：10.1016/j.tet.2010.05.048

  日期：2010.8

  A catalytic intramolecular Heck reaction, followed by capture of the resulting η3-allylpalladium intermediate by a tethered diketopiperazine, is the central step in a concise synthetic route to (−)-spirotryprostatin B and three stereoisomers. This study demonstrates that an acyclic, chiral η3-allylpalladium fragment generated in a catalytic asymmetric Heck cyclization can be trapped by even a weakly

  催化分子内 Heck 反应，然后通过束缚的二酮哌嗪捕获所得的 η 3 -烯丙基钯中间体，是 (-)-螺环前列腺素 B 和三种立体异构体的简洁合成路线中的核心步骤。该研究表明，在催化不对称 Heck 环化中产生的无环手性 η 3 -烯丙基钯片段，即使是弱亲核性的二酮哌嗪也可以比非对映体平衡更快地捕获。
• Palladium-Catalyzed Regio- and Enantioselective Allylic Alkylation of Bis Allylic Carbonates Derived from Morita−Baylis−Hillman Adducts
  作者：Barry M. Trost、Megan K. Brennan

  DOI：10.1021/ol701585b

  日期：2007.9.1

  Morita-Baylis-Hillman diene adducts are used as substrates in the palladium-catalyzed asymmetric allylic alkylation reaction with oxygen and carbon nucleophiles in good regio- and enantioselectivity.

  Morita-Baylis-Hillman二烯加合物用作钯与氧和碳亲核试剂的区域和对映体选择性良好的钯催化不对称烯丙基烷基化反应的底物。
• Total Synthesis of (−)-Spirotryprostatin B and Three Stereoisomers
  作者：Larry E. Overman、Mark D. Rosen

  DOI：10.1002/1521-3773(20001215)39:24<4596::aid-anie4596>3.0.co;2-f

  日期：2000.12.15

  resulting η(3)-allylpalladium intermediate by a tethered diketopiperazine, is the central step in a concise synthetic route to (-)-spirotryprostatin B and three stereoisomers. This study demonstrates that an acyclic, chiral η(3)-allylpalladium fragment generated in a catalytic asymmetric Heck cyclization can be trapped by even a weakly nucleophilic diketopiperazine more rapidly than it undergoes diastereomeric

  催化分子内 Heck 反应，随后通过束缚二酮哌嗪捕获所得的 η(3)-烯丙基钯中间体，是 (-)-spirotryprostatin B 和三种立体异构体的简明合成路线中的核心步骤。这项研究表明，在催化不对称 Heck 环化中生成的无环、手性 η(3)-烯丙基钯片段可以被甚至弱亲核性二酮哌嗪更快地捕获，而不是经历非对映体平衡。
• A Novel Route to Substituted Trienes and Tetraenes
  作者：Tomasz Janecki

  DOI：10.1080/00397919308009822

  日期：1993.3.1

  The reaction sequence involving Arbuzov rearrangement of allyl phosphites 4 to phosphonates 5 followed by Horner-Wadsworth-Emmons olefination of 5 with aldehydes gives substituted trienes and tetraenes 8 with full stereoselectivity.
• Baylis–Hillman reaction in [bdmim][PF 6 ] ionic liquid
  作者：Jen-Chuah Hsu、Ya-Hew Yen、Yen-Ho Chu

  DOI：10.1016/j.tetlet.2004.04.099

  日期：2004.6

  A new use of ionic liquid [bdmim][PF6] as solvent for the Baylis-Hillman reaction is presented. Unlike the commonly used [bmim][PF6] that evidently reacts with electrophilic aldehydes under basic conditions, ionic liquid [bdmim][PF6] is inert and the Baylis-Hillman reaction in [bdmim][PF6] proceeds smoothly with better yield. (C) 2004 Elsevier Ltd. All rights reserved.