(+)-Phenylmenthyl methylacetoacetate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (+)-Phenylmenthyl methylacetoacetate
• 英文别名: [(1S,2R,5S)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] 2-methyl-3-oxobutanoate
• 化学式: C₂₁H₃₀O₃
• 分子量: 330.467
• InChiKey: XVKQNDMVWLDIQW-ZIODWWTISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-Phenylmenthyl methylacetoacetate 在 N,N-二甲基丙烯基脲 、 manganese triacetate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 11.5h， 生成 [(1S,2R,5S)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] (1S,4aR,10aS)-6-methoxy-1,4a-dimethyl-2-oxo-4,9,10,10a-tetrahydro-3H-phenanthrene-1-carboxylate
  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
• 作为产物：
  描述：

  2-甲基乙酰乙酸乙酯 、 (1S,2R,5S)-8-(+)-phenylmenthol 在 4-二甲氨基吡啶 作用下， 以 甲苯 为溶剂， 反应 72.0h， 以90%的产率得到(+)-Phenylmenthyl methylacetoacetate
  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

文献信息

• Asymmetric induction in manganese(III)-based oxidative free-radical cyclizations of phenylmenthyl acetoacetates and 2,5-dimethylpyrrolidine acetoacetamides
  作者：Qingwei Zhang、Raju M. Mohan、Laura Cook、Sophia Kazanis、Daniel Peisach、Bruce M. Foxman、Barry B. Snider

  DOI：10.1021/jo00079a006

  日期：1993.12

  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.