ethyl (E)-6-((tert-butyldimethylsilyl)oxy)-4-methylhex-4-enoate | 960060-34-8

• 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: ethyl (E)-6-((tert-butyldimethylsilyl)oxy)-4-methylhex-4-enoate
• CAS: 960060-34-8
• 化学式: C₁₅H₃₀O₃Si
• 分子量: 286.487
• InChiKey: BYFGLDOYXHSMCK-ACCUITESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  19.0
• 可旋转键数：
  7.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  ethyl (E)-6-((tert-butyldimethylsilyl)oxy)-4-methylhex-4-enoate 在 Shi's ketone N-甲基咪唑 、 oxone 、 四丁基氟化铵 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 二氯甲烷 、 水 、 甲苯 、 乙腈 为溶剂， 生成 tert-butyl ((2R,3R)-3-(2-((2R,3R)-3-(4-methoxy-5,5-diphenylpentyl)-oxiran-2-yl)ethyl)-3-methoxyoxiran-2-yl)methyl carbonate
  参考文献：
  名称：

  An Experimental and Computational Approach to Defining Structure/Reactivity Relationships for Intramolecular Addition Reactions to Bicyclic Epoxonium Ions

  摘要：

  In this manuscript we report that oxidative cleavage reactions can be used to form oxocarbenium ions that react with pendent epoxides to form bicyclic epoxonium ions as an entry to the formation of cyclic oligoether compounds. Bicyclic epoxonium ion structure was shown to have a dramatic impact on the ratio of exo- to endo-cyclization reactions, with bicyclo[4.1.0] intermediates showing a strong preference for endo-closures and bicyclo[3.1.0] intermediates showing a preference for exo-closures. Computational studies on the structures and energetics of the transition states using the B3LYP/6-31G(d) method provide substantial insight into the origins of this selectivity.

  DOI：

  10.1021/ja0709674
• 作为产物：
  描述：

  tert-butyl((3,3-dimethyloxiran-2-yl)methoxy)dimethylsilane 在 2,2,6,6-四甲基哌啶 、 正丁基锂 、 氯化二乙基铝 、 丙酸 作用下， 以 苯 为溶剂， 生成 ethyl (E)-6-((tert-butyldimethylsilyl)oxy)-4-methylhex-4-enoate
  参考文献：
  名称：

  An Experimental and Computational Approach to Defining Structure/Reactivity Relationships for Intramolecular Addition Reactions to Bicyclic Epoxonium Ions

  摘要：

  In this manuscript we report that oxidative cleavage reactions can be used to form oxocarbenium ions that react with pendent epoxides to form bicyclic epoxonium ions as an entry to the formation of cyclic oligoether compounds. Bicyclic epoxonium ion structure was shown to have a dramatic impact on the ratio of exo- to endo-cyclization reactions, with bicyclo[4.1.0] intermediates showing a strong preference for endo-closures and bicyclo[3.1.0] intermediates showing a preference for exo-closures. Computational studies on the structures and energetics of the transition states using the B3LYP/6-31G(d) method provide substantial insight into the origins of this selectivity.

  DOI：

  10.1021/ja0709674

文献信息

• Asymmetric Formation of Allylic Amines with N-Substituted Quaternary Stereocenters by PdII-Catalyzed Aza-Claisen Rearrangements
  作者：Daniel F. Fischer、Zhuo-qun Xin、René Peters

  DOI：10.1002/anie.200702086

  日期：2007.10.8