(+)-(1Z,2R,3S,4S)-1-ethylidene-2,4-dimethyl-5-oxo-3-[(1R)-1-phenylethoxy]-heptyl 2-methylpropanoate | 1258965-37-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+)-(1Z,2R,3S,4S)-1-ethylidene-2,4-dimethyl-5-oxo-3-[(1R)-1-phenylethoxy]-heptyl 2-methylpropanoate
• 英文别名: (+)-(1Z,2R,3S,4S)-1-ethylidene-2,4-dimethyl-5-oxo-3-((1"R)-1-phenylethoxy)heptyl isobutyrate
• CAS: 1258965-37-5
• 化学式: C₂₃H₃₄O₄
• 分子量: 374.521
• InChiKey: UJTLGXCVSHFNNI-OWZMTGNESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.49
• 重原子数：
  27.0
• 可旋转键数：
  10.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (+)-(1Z,2R,3S,4S)-1-ethylidene-2,4-dimethyl-5-oxo-3-[(1R)-1-phenylethoxy]-heptyl 2-methylpropanoate 在 四氯化钛 、 水 、 碳酸氢钠 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以60%的产率得到(2Z,4R,5S,6S)-5-hydroxy-4,6-dimethyl-7-oxonon-2-en-3-yl 2-methylpropanoate
  参考文献：
  名称：

  Total Asymmetric Syntheses of β-Hydroxy-δ-lactones via Umpolung with Sulfur Dioxide

  摘要：

  Cyclic stereotriads and stereotetrads of the beta-hydroxy-delta-lactone type, e.g. prelactones B and E, common in polyketides and polypropionates, are prepared via SO2-induced oxyallylations of enoxysilanes with (1E,3Z)-1-(1-phenylethoxy)penta-1,3-dien-3-yl carboxylates. Using (Z)- or (E)-enoxysilanes both 4,5-cis- or 4,5-trans-delta-lactones are obtained. Depending on the reduction method applied to the obtained aldol intermediates 5,6-trans or 5,6-cis-derivatives are formed. The delta-lactones can be prepared in both their enantiomeric forms depending on the (1R)- or (1S)-configuration of the starting 1-(1-phenylethoxy)penta-1,3-dienes.

  DOI：

  10.1021/jo102035d
• 作为产物：
  描述：

  三甲基(戊-2-烯-3-氧基)硅烷 、 [(1E,3Z)-2-methyl-1-[(1R)-1-phenylethoxy]penta-1,3-dien-3-yl] 2-methylpropanoate 在 二氧化硫 、 双三氟甲烷磺酰亚胺 、 烯丙基三甲基硅烷 、 palladium diacetate 、 potassium carbonate 、 三苯基膦 作用下， 以 二氯甲烷 、 甲苯 、 异丙醇 、 乙腈 为溶剂， 以71%的产率得到(+)-(1Z,2R,3S,4S)-1-ethylidene-2,4-dimethyl-5-oxo-3-[(1R)-1-phenylethoxy]-heptyl 2-methylpropanoate
  参考文献：
  名称：

  Total Asymmetric Syntheses of β-Hydroxy-δ-lactones via Umpolung with Sulfur Dioxide

  摘要：

  Cyclic stereotriads and stereotetrads of the beta-hydroxy-delta-lactone type, e.g. prelactones B and E, common in polyketides and polypropionates, are prepared via SO2-induced oxyallylations of enoxysilanes with (1E,3Z)-1-(1-phenylethoxy)penta-1,3-dien-3-yl carboxylates. Using (Z)- or (E)-enoxysilanes both 4,5-cis- or 4,5-trans-delta-lactones are obtained. Depending on the reduction method applied to the obtained aldol intermediates 5,6-trans or 5,6-cis-derivatives are formed. The delta-lactones can be prepared in both their enantiomeric forms depending on the (1R)- or (1S)-configuration of the starting 1-(1-phenylethoxy)penta-1,3-dienes.

  DOI：

  10.1021/jo102035d

文献信息

• Total Synthesis and Determination of the Absolute Configuration of (−)-Dolabriferol
  作者：Sylvain Laclef、Maris Turks、Pierre Vogel

  DOI：10.1002/anie.201003735

  日期：2010.11.2

  A reaction cascade combining sulfur dioxide with a 1‐oxy‐1,3‐diene and (E)‐silyl enol ether formed the basis of a short total synthesis of (−)‐dolabriferol (see scheme; TMS=trimethylsilyl). The absolute configuration of this natural product, which was first extracted from a gastropod mollusc in 1996, was established unequivocally.

  由二氧化硫与1-氧-1,3-二烯和（E）-甲硅烷基烯醇醚组成的反应级联反应是（-）-二十碳四烯酚短总合成的基础（参见方案; TMS =三甲基甲硅烷基）。明确确定了这种天然产物的绝对构型，该构型最早于1996年从腹足类软体动物中提取。