methyl 6-hydroxy-5,5-dimethyl-3-hexanoate | 110595-98-7

• 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 6-hydroxy-5,5-dimethyl-3-hexanoate
• 英文别名: Methyl 5,5-dimethyl-6-hydroxyhexanoate；Methyl 6-hydroxy-5,5-dimethylhexanoate
• CAS: 110595-98-7
• 化学式: C₉H₁₈O₃
• 分子量: 174.24
• InChiKey: VLSXFAQNQKIOBV-UHFFFAOYSA-N

物化性质

• 沸点：
  227.4±23.0 °C(Predicted)
• 密度：
  0.978±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 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 6-hydroxy-5,5-dimethyl-3-hexanoate 在 六甲基磷酰三胺 、 sodium methylate 、 二异丁基氢化铝 、 三乙胺 、 三氟乙酸酐 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 15.17h， 生成 (7E)-1-hydroxy-2,2,8,12-tetramethyl-5-methylen-7,11-tridecadiene
  参考文献：
  名称：

  鼠薄荷素的合成

  摘要：

  3-苯甲氧基-3,3-二甲基丙醛（）在八个方便的步骤中转化为C 18-醛中间体。在缺少C中的合成的主要步骤7 -单元是乙酰乙酸甲酯和磷酸酯衍生物的顺式选择性甲基化γ-alkoxyethylation 。中间体和通过已知方法转化为月桂烯醇（）。

  DOI：

  10.1016/s0040-4020(01)96076-4
• 作为产物：
  描述：

  Ethyl (E)-6-tert-butyldimethylsilyloxy-5,5-dimethylhex-2-enoate 在 氢氟酸 、 magnesium 作用下， 以 乙腈 为溶剂， 反应 66.0h， 生成 methyl 6-hydroxy-5,5-dimethyl-3-hexanoate
  参考文献：
  名称：

  信息素合成，CCVIII：(1S,3S,7R)-3-Methyl-α-himachalene 的合成，巴西 Jacobina 长须白蛉的性信息素

  摘要：

  (通过采用 Evan 或 Oppolzer 的不对称甲基化和分子内 Diels-Alder 反应这两个关键步骤，对映体选择性地合成了 (1S,3S,7R)-3-甲基-δ-himachalene，它是巴西雅各比纳雄性沙蝇（Lutzomyia longipalpis）的性信息素。通过对与合成中间体之一相关的化合物进行 X 射线分析，明确确定了产物的绝对构型。这种沙蝇信息素的环结具有与已知植物来源的(1R,7R)-δ-himachalene相反的绝对构型。

  DOI：

  10.1055/s-2000-8220

文献信息

• 10.1002/anie.202402858
  作者：Chan, Siu-Chung、Palone, Andrea、Bietti, Massimo、Costas, Miquel

  DOI：10.1002/anie.202402858

  日期：——

  AbstractThe tert‐butyl group is a common aliphatic motif extensively employed to implement steric congestion and conformational rigidity in organic and organometallic molecules. Because of the combination of a high bond dissociation energy (~100 kcal mol−1) and limited accessibility, in the absence of directing groups, neither radical nor organometallic approaches are effective for the chemical modification of tert‐butyl C−H bonds. Herein we overcome these limits by employing a highly electrophilic manganese catalyst, [Mn(CF3bpeb)(OTf)2], that operates in the strong hydrogen bond donor solvent nonafluoro‐tert‐butyl alcohol (NFTBA) and catalytically activates hydrogen peroxide to generate a powerful manganese‐oxo species that effectively oxidizes tert‐butyl C−H bonds. Leveraging on the interplay of steric, electronic, medium and torsional effects, site‐selective and product chemoselective hydroxylation of the tert‐butyl group is accomplished with broad reaction scope, delivering primary alcohols as largely dominant products in preparative yields. Late‐stage hydroxylation at tert‐butyl sites is demonstrated on 6 densely functionalized molecules of pharmaceutical interest. This work uncovers a novel disconnection approach, harnessing tert‐butyl as a potential functional group in strategic synthetic planning for complex molecular architectures.
• Synthesis of moenocinol
  作者：Michael C. Stumpp、Richard R. Schmidt

  DOI：10.1016/s0040-4020(01)96076-4

  日期：1986.1

  3-dimethylpropanal () is converted in eight convenient steps into C18-aldehyde intermediate . Main steps in the synthesis of the missing C7-unit were γ-alkoxyethylation of methyl acetoacetate and cis-selective methylation of the phosphate derivative . Intermediates and are converted to moenocinol () via a known procedure.

  3-苯甲氧基-3,3-二甲基丙醛（）在八个方便的步骤中转化为C 18-醛中间体。在缺少C中的合成的主要步骤7 -单元是乙酰乙酸甲酯和磷酸酯衍生物的顺式选择性甲基化γ-alkoxyethylation 。中间体和通过已知方法转化为月桂烯醇（）。
• Pheromone Synthesis, CCVIII: Synthesis of (1S,3S,7R)-3-Methyl-α-himachalene, the Sex Pheromone of the Sandfly Lutzomyia longipalpis from Jacobina, Brazil
  作者：Takuya Tashiro、Masahiko Bando、Kenji Mori

  DOI：10.1055/s-2000-8220

  日期：——

  (1S,3S,7R)-3-Methyl-α-himachalene, the sex pheromone of the male sandfly (Lutzomyia longipalpis) from Jacobina, Brazil, was synthesized enantioselectively by employing Evan's or Oppolzer's asymmetric methylation and intramolecular Diels-Alder reaction as the two key steps. The absolute configuration of the product was unambiguously established by X-ray analysis of a compound related to one of the synthetic intermediates. The ring junction of this sandfly pheromone possesses the absolute configuration opposite to that of the known (1R,7R)-α-himachalene of plant origin.

  (通过采用 Evan 或 Oppolzer 的不对称甲基化和分子内 Diels-Alder 反应这两个关键步骤，对映体选择性地合成了 (1S,3S,7R)-3-甲基-δ-himachalene，它是巴西雅各比纳雄性沙蝇（Lutzomyia longipalpis）的性信息素。通过对与合成中间体之一相关的化合物进行 X 射线分析，明确确定了产物的绝对构型。这种沙蝇信息素的环结具有与已知植物来源的(1R,7R)-δ-himachalene相反的绝对构型。