(1S,6S)-2-Oxo-6-((E)-propenyl)-1-propyl-cyclohexanecarboxylic acid methyl ester

• 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: (1S,6S)-2-Oxo-6-((E)-propenyl)-1-propyl-cyclohexanecarboxylic acid methyl ester
• 英文别名: methyl (1S,6S)-2-oxo-6-[(E)-prop-1-enyl]-1-propylcyclohexane-1-carboxylate
• 化学式: C₁₄H₂₂O₃
• 分子量: 238.327
• InChiKey: ONEIVPQYCOVGKU-ZHVYSYIMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  methyl (Z)-3-oxo-2-propyldec-7-enoate 在 copper diacetate 、 manganese triacetate 作用下， 以 溶剂黄146 为溶剂， 生成 (1R,6S)-2-Oxo-1-((E)-propenyl)-6-propyl-cyclohexanecarboxylic acid methyl ester 、 2-Oxo-1-propyl-6-prop-(E)-ylidene-cyclohexanecarboxylic acid methyl ester 、 (1S,6S)-2-Oxo-6-((E)-propenyl)-1-propyl-cyclohexanecarboxylic acid methyl ester 、 (1S,6R)-2-Oxo-6-((E)-propenyl)-1-propyl-cyclohexanecarboxylic acid methyl ester
  参考文献：
  名称：

  Asymmetric induction in manganese(III)-based oxidative free-radical cyclizations of phenylmenthyl acetoacetates and 2,5-dimethylpyrrolidine acetoacetamides

  摘要：

  Mn(III)-based oxidative free-radical cyclization of phenylmenthyl ester 1e afforded 90% of 13 with 86% de. Cyclization of 31b provided 56% of (+)-podocarpic acid precursor 32e with 82% de. The direction of de was opposite in these two cases. Oxidative cyclization of a-methyl beta-keto ester 44b gave a 1:1.6 mixture of 46b and 47b while alpha-propyl beta-keto ester 44d produced a > 10:1 mixture of 46d and 47d indicating that the extent and direction of de is dependent on the size of the alpha-substituent The reaction proceeds through transition states 12 and 56 with large alpha-substituents and through transition states 19 and 57 with small a-substituents. The de depends on the double-bond substitution pattern as shown by the decreased de with 37b and 37d, and selectivity in the 5-exo cyclization of 64b, 65b, 70b, and 71b is low.

  DOI：

  10.1021/jo00079a006