(+/-)-(E)-1-hydroxy-1-(4-methoxyphenyl)hex-4-en-3-one | 872427-96-8

• 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: (+/-)-(E)-1-hydroxy-1-(4-methoxyphenyl)hex-4-en-3-one
• 英文别名: (E)-1-hydroxy-1-(4-methoxyphenyl)hex-4-en-3-one
• CAS: 872427-96-8
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: PFSOMJBXGBPFBW-ONEGZZNKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  (+/-)-(E)-1-hydroxy-1-(4-methoxyphenyl)hex-4-en-3-one 在 Hoveyda-Grubbs catalyst second generation N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 (+/-)-4-(tert-butyldimethylsilyloxy)-1-cyclohexylidene-4-(4-methoxyphenyl)butan-2-one
  参考文献：
  名称：

  Elongation of β-hydroxyenones by cross-metathesis

  摘要：

  Enantioenriched aldol products derived from enones are notoriously difficult to prepare due to their sensitivity to retroaldolisation, elimination and the requirement of a large excess of the enone donor for their preparation. However, some success has been obtained for the preparation of aldol products derived from methylvinylketone and penterione using zinc-dinuclear catalysts or catalytic antibodies. Herein, we describe how simple first-generation hydroxyenones can be easily elongated by alkene exchange with structurally diverse olefinic partners in the presence of Ru-based metathesis catalysts allowing for the preparation of aldol products difficult to access by direct aldolisation. The data suggest that even though unprotected aldols are suitable for these cross-metatbesis reactions, silyl-protected beta-hydroxyenones generally afforded the desired elongated products in much higher chemical yields. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.10.037
• 作为产物：
  描述：

  4-甲氧基苯甲醛 、 戊-3-烯-2-酮 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 0.75h， 以66%的产率得到(+/-)-(E)-1-hydroxy-1-(4-methoxyphenyl)hex-4-en-3-one
  参考文献：
  名称：

  对映体富集的四氢和二氢吡喃酮的催化不对称生物有机途径

  摘要：

  描述了一种概念上新颖的羰基化合物异狄尔斯-阿尔德加合物方法，其关键步骤是抗体介导的羟基烯酮动力学拆分，然后是闭环过程。各种 β-羟基烯酮被证明是抗体 84G3 和 93F3 催化的逆羟醛反应的非常好的底物，允许制备高度对映异构体富集（高达 99% ee）的吡喃酮前体。这种方法的一个吸引人的特点是可以通过传统的迈克尔型加成程序将这些无环对映体富集的 β-羟基烯酮转化为四氢吡喃酮，或者使用替代的钯催化氧化闭环转化为相应的二氢吡喃酮。对于钯介导的环化，已经实施了双相系统，该系统允许使用顺序抗体拆分/钯环化策略从相应的外消旋醛醇前体直接制备对映纯二氢吡喃酮，而无需分离中间体对映体富集的羟基烯酮。这种生物有机途径最适用于制备杂狄尔斯-阿尔德加合物，否则衍生自亲核性较低的二烯和未活化的亲二烯体。

  DOI：

  10.1021/ja043925d

文献信息

• A Catalytic Asymmetric Bioorganic Route to Enantioenriched Tetrahydro- and Dihydropyranones
  作者：Charles Baker-Glenn、Neil Hodnett、Maud Reiter、Sandrine Ropp、Rachael Ancliff、Véronique Gouverneur

  DOI：10.1021/ja043925d

  日期：2005.2.1

  A conceptually novel approach to hetero Diels-Alder adducts of carbonyl compounds is described using as the key steps an antibody-mediated kinetic resolution of hydroxyenones followed by a ring-closure process. Various beta-hydroxyenones proved to be very good substrates for antibodies 84G3- and 93F3-catalyzed retro-aldol reactions, allowing the preparation of highly enantiomerically enriched (up to

  描述了一种概念上新颖的羰基化合物异狄尔斯-阿尔德加合物方法，其关键步骤是抗体介导的羟基烯酮动力学拆分，然后是闭环过程。各种 β-羟基烯酮被证明是抗体 84G3 和 93F3 催化的逆羟醛反应的非常好的底物，允许制备高度对映异构体富集（高达 99% ee）的吡喃酮前体。这种方法的一个吸引人的特点是可以通过传统的迈克尔型加成程序将这些无环对映体富集的 β-羟基烯酮转化为四氢吡喃酮，或者使用替代的钯催化氧化闭环转化为相应的二氢吡喃酮。对于钯介导的环化，已经实施了双相系统，该系统允许使用顺序抗体拆分/钯环化策略从相应的外消旋醛醇前体直接制备对映纯二氢吡喃酮，而无需分离中间体对映体富集的羟基烯酮。这种生物有机途径最适用于制备杂狄尔斯-阿尔德加合物，否则衍生自亲核性较低的二烯和未活化的亲二烯体。
• Elongation of β-hydroxyenones by cross-metathesis
  作者：Franck A. Silva、Véronique Gouverneur

  DOI：10.1016/j.tetlet.2005.10.037

  日期：2005.12

  Enantioenriched aldol products derived from enones are notoriously difficult to prepare due to their sensitivity to retroaldolisation, elimination and the requirement of a large excess of the enone donor for their preparation. However, some success has been obtained for the preparation of aldol products derived from methylvinylketone and penterione using zinc-dinuclear catalysts or catalytic antibodies. Herein, we describe how simple first-generation hydroxyenones can be easily elongated by alkene exchange with structurally diverse olefinic partners in the presence of Ru-based metathesis catalysts allowing for the preparation of aldol products difficult to access by direct aldolisation. The data suggest that even though unprotected aldols are suitable for these cross-metatbesis reactions, silyl-protected beta-hydroxyenones generally afforded the desired elongated products in much higher chemical yields. (c) 2005 Elsevier Ltd. All rights reserved.