(3R,4R,14S)-4-hydroxy-3,14-dimethyl-oxacyclotetradecan-2-one | 109849-41-4

• 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: (3R,4R,14S)-4-hydroxy-3,14-dimethyl-oxacyclotetradecan-2-one
• CAS: 109849-41-4；109906-12-9；109906-15-2；116561-05-8
• 化学式: C₁₅H₂₈O₃
• 分子量: 256.386
• InChiKey: MUYMXLCTGOQDTR-BFHYXJOUSA-N

物化性质

• 沸点：
  410.3±28.0 °C(Predicted)
• 密度：
  0.939±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R,4R,14S)-4-hydroxy-3,14-dimethyl-oxacyclotetradecan-2-one 在 三正丁基氢锡 、 lithium diisopropyl amide 作用下， 生成 2RS, 13SR-dimethyltridecanolide
  参考文献：
  名称：

  Ferreira, J. Tercio B.; Neeland, Edward G.; Ounsworth, James P., Canadian Journal of Chemistry, 1987, vol. 65, p. 2314 - 2315

  摘要：

  DOI：
• 作为产物：
  描述：

  (10'-bromo-2'-decyl)-3-oxobutanoate 在 sodium tetrahydroborate 、 lithium diisopropyl amide 作用下， 生成 (3R,4R,14S)-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

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.
• FERREIRA, J. TERCIO B.;NEELAND, EDWARD G.;OUNSWORTH, JAMES P.;WEILER, LAR+, CAN. J. CHEM., 65,(1987) N 9, 2314-2316
  作者：FERREIRA, J. TERCIO B.、NEELAND, EDWARD G.、OUNSWORTH, JAMES P.、WEILER, LAR+

  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：——
• Stereoselective reductions and alkylations of 14-member ring macrolides
  作者：Edward Neeland、James P Ounsworth、Russell J Sims、Larry Weiler

  DOI：10.1016/s0040-4039(00)95642-9

  日期：1987.1

  3-Oxo-13-tetradecanolide (1) was synthesized by an intramolecular dianion alkylation of (10′-bromo-2′-decyl)-3-oxobutanoate. Lithium tri--butylborohydride reduction of 1 gave the 3*,13* alcohol which underwent a stereoselective dianion alkylation (2 eq LDA, MeI). A conformational model for simple 14-member rings is proposed to account for these stereoselective reactions.

  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。
• Ferreira, J. Tercio B.; Neeland, Edward G.; Ounsworth, James P., Canadian Journal of Chemistry, 1987, vol. 65, p. 2314 - 2315
  作者：Ferreira, J. Tercio B.、Neeland, Edward G.、Ounsworth, James P.、Weiler, Larry

  DOI：——

  日期：——