(+)-exo-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-5-yl acetate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (+)-exo-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-5-yl acetate
• 英文别名: (1S,4R,5R)-1,3,3-Trimethyl-2-oxabicyclo[2.2.2]octan-5-yl acetate；(1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-yl) acetate
• 化学式: C₁₂H₂₀O₃
• 分子量: 212.289
• InChiKey: LUYHJKNQBUWCNY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-exo-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-5-yl acetate 在 4-二甲氨基吡啶 、 lithium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 19.0h， 生成 (+)-exo-1,3,3-trimethyl-2-oxabicyclo[2.2.2]oct-5-yl-(R)-α-methoxy-α-(trifluoromethyl)-phenylacetate
  参考文献：
  名称：

  Enzymatic resolution of the 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane (1,8-cineole) system

  摘要：

  Regioselective oxidation of 1,8-cineole 1 with chromyl acetate according to a literature procedure gave the bicyclic 2-ketocineole 8 as the major product along with the symmetrical diketocineole 9. The bicyclic monoketone was reduced with lithium aluminum hydride followed by exposure to acetyl chloride/DMAP to afford the exo-acetate (+/-)-4b. Pig liver esterase (PLE)-mediated hydrolysis of the racemic acetate provided the alcohol (-)-2b (45%) together with its antipodal acetate (+)-4b (43%) in greater than 99% enantiomeric purity, as determined by analysis of the Mosher's ester derivatives. Iodination of the alcohol exo-(+)-2b, obtained by hydrolysis of the resolved actetate with iodine/triphenylphosphine/imidazole, provided the corresponding endo iodide (-)-12a, which was easily dehydro halogenated with DBU under solvent-free conditions to provide the corresponding cineolene (-)-6 in an overall yield of 6 and 99%. e.e. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00313-0
• 作为产物：
  描述：

  1,8-cineole 在 chromium(VI) oxide 、 porcine liver esterase 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 乙酸酐 作用下， 以 phosphate buffer 、 乙醚 、 二氯甲烷 、 溶剂黄146 为溶剂， 反应 33.5h， 生成 (+)-exo-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-5-yl acetate
  参考文献：
  名称：

  Enzymatic resolution of the 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane (1,8-cineole) system

  摘要：

  Regioselective oxidation of 1,8-cineole 1 with chromyl acetate according to a literature procedure gave the bicyclic 2-ketocineole 8 as the major product along with the symmetrical diketocineole 9. The bicyclic monoketone was reduced with lithium aluminum hydride followed by exposure to acetyl chloride/DMAP to afford the exo-acetate (+/-)-4b. Pig liver esterase (PLE)-mediated hydrolysis of the racemic acetate provided the alcohol (-)-2b (45%) together with its antipodal acetate (+)-4b (43%) in greater than 99% enantiomeric purity, as determined by analysis of the Mosher's ester derivatives. Iodination of the alcohol exo-(+)-2b, obtained by hydrolysis of the resolved actetate with iodine/triphenylphosphine/imidazole, provided the corresponding endo iodide (-)-12a, which was easily dehydro halogenated with DBU under solvent-free conditions to provide the corresponding cineolene (-)-6 in an overall yield of 6 and 99%. e.e. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00313-0

文献信息

• Enzymatic resolution of the 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane (1,8-cineole) system
  作者：Frederick A. Luzzio、Damien Y. Duveau

  DOI：10.1016/s0957-4166(02)00313-0

  日期：2002.6

  Regioselective oxidation of 1,8-cineole 1 with chromyl acetate according to a literature procedure gave the bicyclic 2-ketocineole 8 as the major product along with the symmetrical diketocineole 9. The bicyclic monoketone was reduced with lithium aluminum hydride followed by exposure to acetyl chloride/DMAP to afford the exo-acetate (+/-)-4b. Pig liver esterase (PLE)-mediated hydrolysis of the racemic acetate provided the alcohol (-)-2b (45%) together with its antipodal acetate (+)-4b (43%) in greater than 99% enantiomeric purity, as determined by analysis of the Mosher's ester derivatives. Iodination of the alcohol exo-(+)-2b, obtained by hydrolysis of the resolved actetate with iodine/triphenylphosphine/imidazole, provided the corresponding endo iodide (-)-12a, which was easily dehydro halogenated with DBU under solvent-free conditions to provide the corresponding cineolene (-)-6 in an overall yield of 6 and 99%. e.e. (C) 2002 Elsevier Science Ltd. All rights reserved.