(S)-8-methyl-2-oxaspiro[4.5]dec-7-en-1,6-dione | 158530-95-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-8-methyl-2-oxaspiro[4.5]dec-7-en-1,6-dione
• 英文别名: 2-Oxaspiro[4.5]dec-7-ene-1,6-dione, 8-methyl-, (5S)-；(5S)-8-methyl-2-oxaspiro[4.5]dec-7-ene-1,6-dione
• CAS: 158530-95-1
• 化学式: C₁₀H₁₂O₃
• 分子量: 180.203
• InChiKey: PQQGGNWFHARIPV-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (R)-3-[(Z)-1-(1-phenyl-ethylamino)-ethylidene]-dihydro-furan-2-one 在 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 40.0h， 生成 (S)-8-methyl-2-oxaspiro[4.5]dec-7-en-1,6-dione
  参考文献：
  名称：

  Enantioselective Michael-type reaction of chiral linear α,α-disubstituted secondary enamines

  摘要：

  The enantioselective Michael-type reaction of chiral 2-substituted cyclic imines, reacting as their secondary enamine tautomers, has been extended to a linear ketimine possessing an oxo group on one of the substituents. A single secondary enamine tautomer is observed due to H-bonding of the NH group, thus allowing the reaction to proceed with a high degree of stereoselectivity.

  DOI：

  10.1016/0957-4166(94)80112-6

文献信息

• Regioselective Formation of<i>endo</i>- and<i>exo</i>-Cyclic Enamines: Both Enantio­meric Products Accessible by the Same Chiral Auxiliary
  作者：Jens Christoffers、Burkard Kreidler、Heiko Oertling、Sven Unger、Wolfgang Frey

  DOI：10.1055/s-2003-37513

  日期：——

  The copper-catalyzed conversion of exo-cyclic enamines 4a-c with methyl vinyl ketone (2) yields spirocyclic products 6a-c in a sequence of Michael and aldol reaction. The application of the chiral auxiliary l-valine diethylamide results in the formation of quaternary stereocenters with high enantiomeric excess. The configuration of intermediate imine 5a is determined to be S. Thus, exo-cyclic enamines 4 yield S-configured spiroketones 6, whereas, as shown for spiroketone ent-6c, reaction of endo-cyclic enamines such as 1 generates the opposite configuration in the products applying the same auxiliary l-valine diethylamide 9.

  铜催化的外环亚胺 4a-c 与甲基乙烯基酮 (2) 的转化通过迈克尔反应和 aldol 反应顺序生成螺环产物 6a-c。应用手性辅助剂 L-缬氨酸二乙酰胺可形成具有高对映体过剩的四面体立体中心。中间体亚胺 5a 的构型被确定为 S。因此，外环亚胺 4 生成 S 配置的螺酮 6，而对于螺酮 ent-6c，内环亚胺 1 的反应则生成与产品中相反的构型，仍然使用相同的辅助剂 L-缬氨酸二乙酰胺 9。