(6E,10E)-5-<(Triisopropylsilyl)oxy>-7,11,15-trimethyl-6,10,14-hexadecatrien-2-ynal | 149797-96-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (6E,10E)-5-<(Triisopropylsilyl)oxy>-7,11,15-trimethyl-6,10,14-hexadecatrien-2-ynal
• 英文别名: (6E,10E)-7,11,15-trimethyl-5-tri(propan-2-yl)silyloxyhexadeca-6,10,14-trien-2-ynal
• CAS: 149797-96-6
• 化学式: C₂₈H₄₈O₂Si
• 分子量: 444.773
• InChiKey: VWRDYEAFEKFGQX-WZGXYAEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.56
• 重原子数：
  31
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (6E,10E)-5-<(Triisopropylsilyl)oxy>-7,11,15-trimethyl-6,10,14-hexadecatrien-2-ynal 在 咪唑 、 草酰氯 、 偶氮二甲酸二异丙酯 、 四丁基氟化铵 、 二氯乙基铝 、 L-Selectride 、 potassium carbonate 、 二甲基亚砜 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 34.58h， 生成 rel-(1R,2R,6S,7E,11E)-1-Isopropenyl-6-<(tert-butyldimethylsilyl)oxy>-8,12-dimethyl-7,11-cyclotetradecadien-3-yn-2-ol
  参考文献：
  名称：

  Synthesis of 12-, 14-, and 16-membered propargylic alcohols through Lewis acid-promoted ene cyclization

  摘要：

  The scope of the Lewis acid-promoted ene cyclization has been expanded to include 12-, 14-, and 16-membered rings. Thus, the ynals 1.8, 2.5, and 3.5 undergo efficient type-I cyclization upon addition to 1.0 equiv of EtAlCl2 in CH2Cl2 at -78-degrees-C. The epoxy ynal 4.3 undergoes pinacol rearrangement under these conditions. However, treatment with a 1:1 mixture of Et2AlCl and EtAlCl2 effects conversion to the cyclic products 4.4/4.5 (92:8) in satisfactory yield. Facile type-II cyclizations readily achieved with ynals 5.7, 6.4, 7.6, and 8.3 with EtAlCl2 as the Lewis acid. In the latter case, a 16-membered propargylic alcohol was produced in 84% yield.

  DOI：

  10.1021/jo00067a024
• 作为产物：
  描述：

  Farnesal 在 2,6-二甲基吡啶 、 正丁基锂 、 草酰氯 、 magnesium 、 二甲基亚砜 、 三乙胺 、 mercury dichloride 作用下， 以 二氯甲烷 为溶剂， 反应 8.92h， 生成 (6E,10E)-5-<(Triisopropylsilyl)oxy>-7,11,15-trimethyl-6,10,14-hexadecatrien-2-ynal
  参考文献：
  名称：

  Synthesis of 12-, 14-, and 16-membered propargylic alcohols through Lewis acid-promoted ene cyclization

  摘要：

  The scope of the Lewis acid-promoted ene cyclization has been expanded to include 12-, 14-, and 16-membered rings. Thus, the ynals 1.8, 2.5, and 3.5 undergo efficient type-I cyclization upon addition to 1.0 equiv of EtAlCl2 in CH2Cl2 at -78-degrees-C. The epoxy ynal 4.3 undergoes pinacol rearrangement under these conditions. However, treatment with a 1:1 mixture of Et2AlCl and EtAlCl2 effects conversion to the cyclic products 4.4/4.5 (92:8) in satisfactory yield. Facile type-II cyclizations readily achieved with ynals 5.7, 6.4, 7.6, and 8.3 with EtAlCl2 as the Lewis acid. In the latter case, a 16-membered propargylic alcohol was produced in 84% yield.

  DOI：

  10.1021/jo00067a024

文献信息

• Synthesis of 12-, 14-, and 16-membered propargylic alcohols through Lewis acid-promoted ene cyclization
  作者：James A. Marshall、Marc W. Andersen

  DOI：10.1021/jo00067a024

  日期：1993.7

  The scope of the Lewis acid-promoted ene cyclization has been expanded to include 12-, 14-, and 16-membered rings. Thus, the ynals 1.8, 2.5, and 3.5 undergo efficient type-I cyclization upon addition to 1.0 equiv of EtAlCl2 in CH2Cl2 at -78-degrees-C. The epoxy ynal 4.3 undergoes pinacol rearrangement under these conditions. However, treatment with a 1:1 mixture of Et2AlCl and EtAlCl2 effects conversion to the cyclic products 4.4/4.5 (92:8) in satisfactory yield. Facile type-II cyclizations readily achieved with ynals 5.7, 6.4, 7.6, and 8.3 with EtAlCl2 as the Lewis acid. In the latter case, a 16-membered propargylic alcohol was produced in 84% yield.