2-Allyl-6-methyl-3-oxo-hept-6-enoic acid (1S,2R,3S,4S)-4,7,7-trimethyl-3-naphthalen-2-yl-bicyclo[2.2.1]hept-2-yl ester | 144764-71-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-Allyl-6-methyl-3-oxo-hept-6-enoic acid (1S,2R,3S,4S)-4,7,7-trimethyl-3-naphthalen-2-yl-bicyclo[2.2.1]hept-2-yl ester
• 英文别名: [(1S,2R,3S,4S)-4,7,7-trimethyl-3-naphthalen-2-yl-2-bicyclo[2.2.1]heptanyl] 6-methyl-3-oxo-2-prop-2-enylhept-6-enoate
• CAS: 144764-71-6
• 化学式: C₃₁H₃₈O₃
• 分子量: 458.641
• InChiKey: CDXMUUGDIQBGQR-KSCYKUDKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.4
• 重原子数：
  34
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.48
• 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：

  2-Allyl-6-methyl-3-oxo-hept-6-enoic acid (1S,2R,3S,4S)-4,7,7-trimethyl-3-naphthalen-2-yl-bicyclo[2.2.1]hept-2-yl ester 在 copper diacetate 、 manganese triacetate 作用下， 以 溶剂黄146 为溶剂， 以87%的产率得到(1S,5R)-5-Methyl-6-methylene-2-oxo-bicyclo[3.2.1]octane-1-carboxylic acid (1S,2R,3S,4S)-4,7,7-trimethyl-3-naphthalen-2-yl-bicyclo[2.2.1]hept-2-yl 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
• 作为产物：
  描述：

  methyl 2-(2-propenyl)-3-oxo-6-methylhept-6-enoate 、 exo-3-hydroxy-exo-2-(β-naphthyl)bornane 在 4-二甲氨基吡啶 作用下， 以 甲苯 为溶剂， 生成 2-Allyl-6-methyl-3-oxo-hept-6-enoic acid (1S,2R,3S,4S)-4,7,7-trimethyl-3-naphthalen-2-yl-bicyclo[2.2.1]hept-2-yl ester
  参考文献：
  名称：

  基于锰（III）的手性酯和酰胺的氧化自由基环化中的不对称诱导

  摘要：

  乙酰薄荷基乙酸薄荷酯1d的基于Mn（III）的氧化自由基环化反应得到90％的11和86％的de。反式-2-苯基环己基酯1e得到的de只有60％的5e。2,5-二甲基吡咯烷酰胺1H，得到14具有较高的德（92％），但在仅28％的产率。

  DOI：

  10.1016/s0040-4039(00)61089-4

文献信息

• Asymmetric induction in Manganese(III)-based oxidative free-radical cyclizations of chiral esters and amides
  作者：Barry B. Snider、Qingwei Zhang

  DOI：10.1016/s0040-4039(00)61089-4

  日期：1992.9

  Mn(III)-based oxidative free-radical cyclizations of phenylmenthyl acetoacetate 1d affords 90% of 11 with 86% de. trans-2-Phenylcyclohexyl ester 1e affords 5e with only 60% de. The 2,5-dimethylpyrrolidine amide 1h affords 14 with higher de (92%), but in only 28% yield.

  乙酰薄荷基乙酸薄荷酯1d的基于Mn（III）的氧化自由基环化反应得到90％的11和86％的de。反式-2-苯基环己基酯1e得到的de只有60％的5e。2,5-二甲基吡咯烷酰胺1H，得到14具有较高的德（92％），但在仅28％的产率。
• 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.