3-Oxo-13-tetradecanolide | 85920-80-5

• 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: 3-Oxo-13-tetradecanolide
• 英文别名: 3-Oxotetradecan-13-olide；14-Methyl-oxacyclotetradecane-2,4-dione
• CAS: 85920-80-5
• 化学式: C₁₄H₂₄O₃
• 分子量: 240.343
• InChiKey: DNYBKSGGJOWOGL-UHFFFAOYSA-N

物化性质

• 沸点：
  403.4±28.0 °C(Predicted)
• 密度：
  0.952±0.06 g/cm3(Predicted)

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：

  3-Oxo-13-tetradecanolide 在 sodium tetrahydroborate 作用下， 生成 (3R,4R,14R)-4-hydroxy-3,14-dimethyl-oxacyclotetradecan-2-one
  参考文献：
  名称：

  14元环大环内酯类化合物的立体选择性还原和烷基化

  摘要：

  通过（10'-溴-2'-癸基）-3-氧代丁酸酯的分子内二价阴离子烷基化反应合成3-Oxo-13-十四烷酸酯（1）。三-丁基硼氢化锂还原为1，得到3 *，13 *醇，该醇进行了立体选择性二价阴离子烷基化反应（2 eq LDA，MeI）。为了解决这些立体选择性反应，提出了一个简单的14元环构象模型。

  DOI：

  10.1016/s0040-4039(00)95642-9
• 作为产物：
  描述：

  2-十一烯酸 在 sodium tetrahydroborate 、 jones reagent 、 mercury(II) diacetate 、 溴 、 mercury(II) oxide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 为溶剂， 反应 30.83h， 生成 3-Oxo-13-tetradecanolide
  参考文献：
  名称：

  Lermer, Leonard; Neeland, Edward G.; Ounsworth, James P., Canadian Journal of Chemistry, 1992, vol. 70, # 5, p. 1427 - 1445

  摘要：

  DOI：

文献信息

• Lactone synthesis via the intramolecular alkylation of β-keto ester dianions
  作者：Russell J. Sims、Samuel A. Tischler、Larry Weiler

  DOI：10.1016/s0040-4039(00)81378-7

  日期：1983.1

  Long chain ω-halo β-keto esters undergo intramolecular alkylation via the dianions to yield macrocylic β-keto lactones.

  长链ω-卤代β-酮酯通过二价阴离子进行分子内烷基化反应，生成大环β-酮内酯。
• Alkylation of the dianion of 3-oxo-13-tetradecanolide
  作者：Edward G. Neeland、Anurag Sharadendu、Larry Weiler

  DOI：10.1016/0040-4039(96)01019-2

  日期：1996.7

  Alkylation of the dianion of 3-oxo-13-tetradecanolide(1) was carried out in high stereoselectivity and chemical yield. The relative stereochemistry of the two distant chiral centers were determined by chemical transformation of 2 to dibenzoates 6 and 7, whose relative stereochemistry was determined using chiral HPLC.

  3-氧代-13-十四烷酸酯（1）的二价阴离子的烷基化反应具有很高的立体选择性和化学收率。通过将2转化为二苯甲酸酯6和7来确定两个遥远手性中心的相对立体化学，使用手性HPLC测定其相对立体化学。
• 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.
• SIMS, R. J.;TISCHLER, S. A.;WEILER, L., TETRAHEDRON LETT., 0.083, 24, N 3, 253-256
  作者：SIMS, R. J.、TISCHLER, S. A.、WEILER, L.

  DOI：——

  日期：——
• NEELAND E.; OUNSWORTH J. P.; SIMS R. J.; WEILER L., TETRAHEDRON LETT., 28,(1987) N 1, 35-38
  作者：NEELAND E.、 OUNSWORTH J. P.、 SIMS R. J.、 WEILER L.

  DOI：——

  日期：——