methyl (2S,3R,E)-3-(tert-butyldimethylsiloxy)-2-((E)-prop-1-enyl)hex-4-enoate | 827605-74-3

• 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 (2S,3R,E)-3-(tert-butyldimethylsiloxy)-2-((E)-prop-1-enyl)hex-4-enoate
• 英文别名: methyl (E,2S,3R)-3-[tert-butyl(dimethyl)silyl]oxy-2-[(E)-prop-1-enyl]hex-4-enoate
• CAS: 827605-74-3
• 化学式: C₁₆H₃₀O₃Si
• 分子量: 298.498
• InChiKey: QUABSZOASOVAEA-HOOKYRBSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.32
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (2S,3R,E)-3-(tert-butyldimethylsiloxy)-2-((E)-prop-1-enyl)hex-4-enoate 在 1-ethyl-3-methyl-1H-imidazolium salt 作用下， 以 various solvent(s) 为溶剂， 反应 0.75h， 生成 methyl (4S,5R,E)-4,5-dimethyl-7-oxohept-2-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
• 作为产物：
  描述：

  trans-crotyl tert-butyldimethylsilyl ether 、 methyl (E)-2-diazopent-3-enoate 在 dirhodium tetrakis(S-(N-dodecylbenzenesulfonyl)prolinate) 作用下， 以 various solvent(s) 为溶剂， 反应 4.5h， 生成 methyl (2E,4S,5R,6Z)-7-(tert-butyldimethylsiloxy)-4,5-dimethylhepta-2,6-dienoate 、 methyl (2E,4R,5S,6Z)-7-(tert-butyldimethylsiloxy)-4,5-dimethylhepta-2,6-dienoate 、 methyl (2S,3R,E)-3-(tert-butyldimethylsiloxy)-2-((E)-prop-1-enyl)hex-4-enoate 、 methyl (2R,3S,E)-3-(tert-butyldimethylsiloxy)-2-((E)-prop-1-enyl)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.