(-)-menthyl (1S,5S)-2-oxobicyclo[3.1.0]hexane-1-carboxylate | 74965-61-0

• 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: (-)-menthyl (1S,5S)-2-oxobicyclo[3.1.0]hexane-1-carboxylate
• 英文别名: [(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] (1S,5S)-2-oxobicyclo[3.1.0]hexane-1-carboxylate
• CAS: 74965-61-0
• 化学式: C₁₇H₂₆O₃
• 分子量: 278.392
• InChiKey: UFPGXMDIMPFPAI-KAHPBISDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  (-)-menthyl (1S,5S)-2-oxobicyclo[3.1.0]hexane-1-carboxylate 在 copper(l) iodide 、 sodium cyanoborohydride 、 对甲苯磺酰肼 、 zinc(II) chloride 作用下， 反应 66.25h， 生成 (R)-2-Pentyl-cyclopentanecarboxylic acid (1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl ester
  参考文献：
  名称：

  Rhodium-Mediated Intramolecular C−H Insertion:  Probing the Geometry of the Transition State

  摘要：

  The unsymmetrical alpha-diazo ester 1b, derived from the chiral naphthylborneol 5, was cyclized with a set of rhodium carboxylates (L = CF3CO2, CH3CO2, CH3(CH2)(6)CO2, (CH3)(3)CCO2). The ratio of the three major products ((R,R)-3b, (S,S)-3b, 4b) was determined. It was found that the rhodium catalyst derived from pivalic acid gave the highest ratio of 3b:4b. Lowering the temperature of the reaction (L = (CH3)(3)CCO2) increased both the yield and the diastereoselectivity of the cyclization. From these results and from our computational analysis, it is concluded that the ester carbonyl and the rhodium carbenoid are probably syn in the transition state leading to cyclization.

  DOI：

  10.1021/jo9803434
• 作为产物：
  描述：

  3-氧代丁酸 (1R,2S,5R)-5-甲基-2-(1-甲基乙基)环己基酯 在 正丁基锂 、 对甲苯磺酰叠氮 、 TEA 、 铜 、 sodium hydride 作用下， 反应 1.5h， 生成 (-)-menthyl (1S,5S)-2-oxobicyclo[3.1.0]hexane-1-carboxylate
  参考文献：
  名称：

  Preparation of cyclohexanones and cyclopentanones of high optical purity

  摘要：

  DOI：

  10.1021/jo01311a031

文献信息

• Nemoto, Hideo; Kimura, Toshihiko; Kurobe, Hiroshi, Journal of the Chemical Society. Perkin transactions I, 1986, p. 1777 - 1780
  作者：Nemoto, Hideo、Kimura, Toshihiko、Kurobe, Hiroshi、Fukumoto, Keiichiro、Kametani, Tetsuji

  DOI：——

  日期：——
• Preparation of cyclohexanones and cyclopentanones of high optical purity
  作者：Douglass F. Taber、Samir A. Saleh、Richard W. Korsmeyer

  DOI：10.1021/jo01311a031

  日期：1980.11
• Rhodium-Mediated Intramolecular C−H Insertion:  Probing the Geometry of the Transition State
  作者：Douglass F. Taber、Scott C. Malcolm

  DOI：10.1021/jo9803434

  日期：1998.5.1

  The unsymmetrical alpha-diazo ester 1b, derived from the chiral naphthylborneol 5, was cyclized with a set of rhodium carboxylates (L = CF3CO2, CH3CO2, CH3(CH2)(6)CO2, (CH3)(3)CCO2). The ratio of the three major products ((R,R)-3b, (S,S)-3b, 4b) was determined. It was found that the rhodium catalyst derived from pivalic acid gave the highest ratio of 3b:4b. Lowering the temperature of the reaction (L = (CH3)(3)CCO2) increased both the yield and the diastereoselectivity of the cyclization. From these results and from our computational analysis, it is concluded that the ester carbonyl and the rhodium carbenoid are probably syn in the transition state leading to cyclization.