methyl (4R,5S,E)-5-methyl-7-oxo-4-phenylhept-2-enoate | 827605-78-7

• 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: methyl (4R,5S,E)-5-methyl-7-oxo-4-phenylhept-2-enoate
• 英文别名: methyl (E,4R,5S)-5-methyl-7-oxo-4-phenylhept-2-enoate
• CAS: 827605-78-7
• 化学式: C₁₅H₁₈O₃
• 分子量: 246.306
• InChiKey: WJLLAYJUVCSIMC-DENSBJQYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.72
• 重原子数：
  18.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  methyl (4R,5S,E)-5-methyl-7-oxo-4-phenylhept-2-enoate 在 3-苄基羟乙基甲基噻唑氯化锂 、 双(三甲基硅烷基)氨基钾 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 24.0h， 以59%的产率得到methyl 2-(3-methyl-5-oxo-2-phenylcyclopentyl)acetate
  参考文献：
  名称：

  Catalytic Asymmetric Reactions for Organic Synthesis:  The Combined C−H Activation/Siloxy-Cope Rearrangement

  摘要：

  Tetrakis(N-[4-dodecylbenzenesulfonyl]-(L)-prolinate) dirhodium [Rh-2(S-DOSP)(4)]-catalyzed decomposition of vinyldiazoacetates in the presence of allyl silyl ethers results in the formation of the direct C-H insertion product and the product derived from a combined C-H activation/siloxy-Cope rearrangement. Both products are formed with very high diastereoselectivity (>94% de) and high enantioselectvity (78-93% ee). Under thermal or microwave conditions, the direct C-H insertion product undergoes a siloxy-Cope rearrangement in a stereoselective manner.

  DOI：

  10.1021/jo048429m
• 作为产物：
  描述：

  trans-1-(trimethylsilyloxy)-2-butene 、 (E)-methyl 2-diazo-4-phenylbut-3-enoate 在 dirhodium tetrakis(S-(N-dodecylbenzenesulfonyl)prolinate) 作用下， 以 various solvent(s) 为溶剂， 反应 2.33h， 生成 methyl (4S,5R,E)-5-methyl-7-oxo-4-phenylhept-2-enoate 、 methyl (4R,5S,E)-5-methyl-7-oxo-4-phenylhept-2-enoate 、 (2R,3S,E)-2-((E)-styryl)-3-(trimethylsiloxy)hex-4-enoate 、 (2S,3R,E)-2-((E)-styryl)-3-(trimethylsiloxy)hex-4-enoate
  参考文献：
  名称：

  Catalytic Asymmetric Reactions for Organic Synthesis:  The Combined C−H Activation/Siloxy-Cope Rearrangement

  摘要：

  Tetrakis(N-[4-dodecylbenzenesulfonyl]-(L)-prolinate) dirhodium [Rh-2(S-DOSP)(4)]-catalyzed decomposition of vinyldiazoacetates in the presence of allyl silyl ethers results in the formation of the direct C-H insertion product and the product derived from a combined C-H activation/siloxy-Cope rearrangement. Both products are formed with very high diastereoselectivity (>94% de) and high enantioselectvity (78-93% ee). Under thermal or microwave conditions, the direct C-H insertion product undergoes a siloxy-Cope rearrangement in a stereoselective manner.

  DOI：

  10.1021/jo048429m

文献信息

• Catalytic Asymmetric Reactions for Organic Synthesis:  The Combined C−H Activation/Siloxy-Cope Rearrangement
  作者：Huw M. L. Davies、Rohan E. J. Beckwith

  DOI：10.1021/jo048429m

  日期：2004.12.1

  Tetrakis(N-[4-dodecylbenzenesulfonyl]-(L)-prolinate) dirhodium [Rh-2(S-DOSP)(4)]-catalyzed decomposition of vinyldiazoacetates in the presence of allyl silyl ethers results in the formation of the direct C-H insertion product and the product derived from a combined C-H activation/siloxy-Cope rearrangement. Both products are formed with very high diastereoselectivity (>94% de) and high enantioselectvity (78-93% ee). Under thermal or microwave conditions, the direct C-H insertion product undergoes a siloxy-Cope rearrangement in a stereoselective manner.