(1R,3R,4S)-8-phenylmenthyl 2-methylacetoacetate | 192199-24-9

• 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: (1R,3R,4S)-8-phenylmenthyl 2-methylacetoacetate
• 英文别名: 8-phenylmenthyl 2-methyl-3-oxobutanoate；(-)-Phenylmenthyl methylacetoacetate；[(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] 2-methyl-3-oxobutanoate
• CAS: 192199-24-9
• 化学式: C₂₁H₃₀O₃
• 分子量: 330.467
• InChiKey: XVKQNDMVWLDIQW-MWDYEWRCSA-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：

  (1R,3R,4S)-8-phenylmenthyl 2-methylacetoacetate 在 盐酸 、 N,N-二甲基丙烯基脲 、 sodium chlorite 、 sodium dihydrogenphosphate 、 lithium aluminium tetrahydride 、 2-甲基-2-丁烯 、 草酰氯 、 manganese triacetate 、 二甲基亚砜 、 三乙胺 、 锌 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 水 、 叔丁醇 为溶剂， 反应 89.33h， 生成 O-methylpodocarpic acid
  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：

  (-)-8-苯基薄荷醇 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 生成 (1R,3R,4S)-8-phenylmenthyl 2-methylacetoacetate
  参考文献：
  名称：

  Diastereoselective alkylation of 8-phenylmenthyl 2-methylacetoacetate. Preparation of enantiomerically pure 4,4-disubstituted 2-pyrazolin-5-ones

  摘要：

  Alkylation of (1R,3R,4S)-8-phenylmenthyl 2-methylacetoacetate with alkyl halides affords 2-alkyl-2-methylacetoacetates in diastereomeric ratios 72:28 to 85:15. The major R (at C-alpha) diastereoisomers are converted into enantiopure 4,4-disubstituted 2-pyrazolin-5-ones with recovery of the chiral inductor. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00131-6

文献信息

• A Convenient Synthesis of A-Ring-Functionalized Podolactones. Revision of the Structure of Wentilactone B
  作者：Alejandro F. Barrero、María M. Herrador、José F. Quílez del Moral、Mónica V. Valdivia

  DOI：10.1021/ol0257070

  日期：2002.4.1

  A new route to podolactones functionalized in the A ring has been achieved. Two key steps were employed in this synthesis, the construction of the bicyclic skeleton via a Mn(III)-mediated radical cyclization and the transformation of this bicyclic intermediate into the tetracyclic podolactone skeleton through a Pd (II)-mediated bislactonization of the corresponding conjugate diene. The reported synthesis

  实现了在A环中官能化的足内酯的新途径。该合成过程中采用了两个关键步骤，即通过Mn（III）介导的自由基环化作用构建双环骨架，以及通过Pd（II）介导的相应共轭物的双内酯化作用将该双环中间体转变为四环足内酯骨架。二烯。报道的3beta-hydroxy-13,14,15,16-tetranorlabda-7,9（11）-dien-（19,6beta），（12,17）-二醇（1）的合成让我们重新分配了甲基内酯的结构B，错误报告了结构1。[反应：看文字]
• Zhang Qingwei, Mohan Raju M., Cook Laura, Kazanis Sophia, Peisach Daniel,+, J. Org. Chem, 58 (1993) N 27, S 7640-7651
  作者：Zhang Qingwei, Mohan Raju M., Cook Laura, Kazanis Sophia, Peisach Daniel,+

  DOI：——

  日期：——
• Diastereoselective Aziridination of Chiral α-Carbonyl Enoates¹
  作者：Stefania Fioravanti、Alberto Morreale、Lucio Pellacani、Paolo A. Tardella

  DOI：10.1021/jo025670x

  日期：2002.7.1

  Nosyloxycarbamates very efficiently aziridinate optically active a-carbonyl enoates with high levels of diastereoselectivity under mild conditions and in a straightforward process.
• 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.
• Diastereoselective alkylation of 8-phenylmenthyl 2-methylacetoacetate. Preparation of enantiomerically pure 4,4-disubstituted 2-pyrazolin-5-ones
  作者：Marcial Moreno-Mañas、Rosa M. Sebastián、Adelina Vallribera、Elies Molins、Enrique Espinosa

  DOI：10.1016/s0957-4166(97)00131-6

  日期：1997.5

  Alkylation of (1R,3R,4S)-8-phenylmenthyl 2-methylacetoacetate with alkyl halides affords 2-alkyl-2-methylacetoacetates in diastereomeric ratios 72:28 to 85:15. The major R (at C-alpha) diastereoisomers are converted into enantiopure 4,4-disubstituted 2-pyrazolin-5-ones with recovery of the chiral inductor. (C) 1997 Elsevier Science Ltd.