(13S)-3-Oxo-13-tetradecanolide | 161813-86-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: (13S)-3-Oxo-13-tetradecanolide
• 英文别名: (14S)-14-methyl-oxacyclotetradecane-2,4-dione
• CAS: 161813-86-1
• 化学式: C₁₄H₂₄O₃
• 分子量: 240.343
• InChiKey: DNYBKSGGJOWOGL-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  (13S)-3-Oxo-13-tetradecanolide 在 偶氮二异丁腈 、 三正丁基氢锡 、 L-Selectride 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 甲苯 为溶剂， 反应 2.0h， 生成 (S)-3-羟基十四烷酸
  参考文献：
  名称：

  Synthesis, Conformational Analysis, and Stereoselective Reduction of 14-Membered Ring 3-Keto Lactones

  摘要：

  The synthesis of 3-oxo-13-tetradecanolide (5) and its 2-methyl and 2,2-dimethyl derivatives 7 and 8 have been carried out. The keto carbonyls in 5, 7, and 8 have been reduced with varying degrees of stereoselectivity. The stereoselectivity of the reduction depends on the counterion with the borohydride reducing agent, but selectivities approaching 100% have been achieved for 5 and 7. The structure of the reduced products were determined by X-ray crystallography and chemical correlation. Heavy reliance on the stereoselectivity in the Frater dianion alkylation was used. The solution conformation of the beta-keto lactones was found to be based on A both from NMR studies and molecular mechanics calculations. However, we are not able to predict the observed stereoselectivity in the hydride reduction of the ketones using this conformation. Thus we suggest the reduction proceeds through conformation B' in which the two carbonyls are chelated to the counterion. The conformations of the resulting alcohols are more complex and have both inter- and intramolecular hydrogen bonding which control the conformations. The use of polar maps to illustrate similarities and differences in conformations is demonstrated. These conformations are used to rationalize the physical and chemical properties of the beta-keto and beta-hydroxy 14-membered lactones.

  DOI：

  10.1021/jo00103a034
• 作为产物：
  描述：

  2-[(7-溴庚基)氧基]四氢-2H-吡喃 在 吡啶 、 copper(l) iodide 、 magnesium 、 溶剂黄146 、 lithium bromide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 22.83h， 生成 (13S)-3-Oxo-13-tetradecanolide
  参考文献：
  名称：

  Synthesis, Conformational Analysis, and Stereoselective Reduction of 14-Membered Ring 3-Keto Lactones

  摘要：

  The synthesis of 3-oxo-13-tetradecanolide (5) and its 2-methyl and 2,2-dimethyl derivatives 7 and 8 have been carried out. The keto carbonyls in 5, 7, and 8 have been reduced with varying degrees of stereoselectivity. The stereoselectivity of the reduction depends on the counterion with the borohydride reducing agent, but selectivities approaching 100% have been achieved for 5 and 7. The structure of the reduced products were determined by X-ray crystallography and chemical correlation. Heavy reliance on the stereoselectivity in the Frater dianion alkylation was used. The solution conformation of the beta-keto lactones was found to be based on A both from NMR studies and molecular mechanics calculations. However, we are not able to predict the observed stereoselectivity in the hydride reduction of the ketones using this conformation. Thus we suggest the reduction proceeds through conformation B' in which the two carbonyls are chelated to the counterion. The conformations of the resulting alcohols are more complex and have both inter- and intramolecular hydrogen bonding which control the conformations. The use of polar maps to illustrate similarities and differences in conformations is demonstrated. These conformations are used to rationalize the physical and chemical properties of the beta-keto and beta-hydroxy 14-membered lactones.

  DOI：

  10.1021/jo00103a034

文献信息

• Synthesis, Conformational Analysis, and Stereoselective Reduction of 14-Membered Ring 3-Keto Lactones
  作者：Edward G. Neeland、James P. Ounsworth、Russel J. Sims、Larry Weiler

  DOI：10.1021/jo00103a034

  日期：1994.12

  The synthesis of 3-oxo-13-tetradecanolide (5) and its 2-methyl and 2,2-dimethyl derivatives 7 and 8 have been carried out. The keto carbonyls in 5, 7, and 8 have been reduced with varying degrees of stereoselectivity. The stereoselectivity of the reduction depends on the counterion with the borohydride reducing agent, but selectivities approaching 100% have been achieved for 5 and 7. The structure of the reduced products were determined by X-ray crystallography and chemical correlation. Heavy reliance on the stereoselectivity in the Frater dianion alkylation was used. The solution conformation of the beta-keto lactones was found to be based on A both from NMR studies and molecular mechanics calculations. However, we are not able to predict the observed stereoselectivity in the hydride reduction of the ketones using this conformation. Thus we suggest the reduction proceeds through conformation B' in which the two carbonyls are chelated to the counterion. The conformations of the resulting alcohols are more complex and have both inter- and intramolecular hydrogen bonding which control the conformations. The use of polar maps to illustrate similarities and differences in conformations is demonstrated. These conformations are used to rationalize the physical and chemical properties of the beta-keto and beta-hydroxy 14-membered lactones.