methyl (2E,4S,5R,6Z)-4-(4-bromophenyl)-7-(tert-butyldimethylsilyloxy)-5-phenylhepta-2,6-dienoate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: methyl (2E,4S,5R,6Z)-4-(4-bromophenyl)-7-(tert-butyldimethylsilyloxy)-5-phenylhepta-2,6-dienoate
• 英文别名: methyl (2E,4S,5R,6Z)-4-(4-bromophenyl)-7-[tert-butyl(dimethyl)silyl]oxy-5-phenylhepta-2,6-dienoate
• 化学式: C₂₆H₃₃BrO₃Si
• 分子量: 501.536
• InChiKey: DIXHBAZDBDHUFY-RZXITWIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.58
• 重原子数：
  31
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 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 (2E,4S,5R,6Z)-4-(4-bromophenyl)-7-(tert-butyldimethylsilyloxy)-5-phenylhepta-2,6-dienoate 、 2,4-二硝基苯肼 在 盐酸 作用下， 以 乙醇 为溶剂， 反应 14.0h， 以87%的产率得到methyl (2E,4S,5S,7E)-4-(4-bromophenyl)-7-(2-(2,4-dinitrophenyl)hydrazono)-5-phenylhept-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：

  (E)-1-tert-butyldimethylsilyloxy-3-phenyl-2-propene 、 (E)-methyl 4-(4-bromophenyl)-2-diazobut-3-enoate 在 Rh₂(R-DOSP)4 作用下， 以 various solvent(s) 为溶剂， 反应 3.33h， 生成 methyl (2S,3R,E)-2-((E)-4-bromostyryl)-3-(tert-butyldimethylsilyloxy)-5-phenylpent-4-enoate 、 methyl (2R,3S,E)-2-((E)-4-bromostyryl)-3-(tert-butyldimethylsilyloxy)-5-phenylpent-4-enoate 、 methyl (2E,4S,5R,6Z)-4-(4-bromophenyl)-7-(tert-butyldimethylsilyloxy)-5-phenylhepta-2,6-dienoate 、 methyl (2E,4R,5S,6Z)-4-(4-bromophenyl)-7-(tert-butyldimethylsilyloxy)-5-phenylhepta-2,6-dienoate
  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.