1,8-cineole

• 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: 1,8-cineole
• 英文别名: 3-Hydroxycineole；1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-ol
• 化学式: C₁₀H₁₈O₂
• 分子量: 170.252
• InChiKey: WHIKIYRWRMRQNK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

ADMET

代谢

3alpha-羟基-1,8-桉树脑是1,8-桉树脑的人类已知代谢物。

3alpha-hydroxy-1,8-cineole is a known human metabolite of 1,8-Cineole.

来源:NORMAN Suspect List Exchange

反应信息

• 作为反应物：
  描述：

  1,8-cineole 在 咪唑 、 碘 、 三苯基膦 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 、 苯 为溶剂， 反应 6.0h， 以62 mg的产率得到1,3,3-三甲基-2-氧杂双环[2.2.2]辛-5-烯
  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：

  4,4,5,5-tetramethyl-2-(1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-yl)-1,3,2-dioxaborolane 在 双氧水 、 sodium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 以67%的产率得到1,8-cineole
  参考文献：
  名称：

  铜介导的烷烃脱氢 C(sp3)–H 硼化反应

  摘要：

  惰性碳氢键的硼化对于将原料化学品转化为多功能有机硼试剂非常有用。这些反应的催化历来依赖于贵金属络合物，其在无氧化剂条件下促进二硼试剂的脱氢硼化反应。最近，涉及氢原子转移途径的光诱导自由基介导的硼基化已成为有吸引力的替代方案，因为它们提供了互补的区域选择性并在无金属条件下进行。然而，这些净氧化过程需要化学计量的氧化剂，因此无法与贵金属催化的对应物的高原子经济性竞争。在此，我们报道了 CuCl 2在无氧化剂条件下催化烷烃与双儿茶酚二硼的自由基介导的脱氢 C(sp 3 )–H 硼化反应。这是铜催化剂意想不到的双重作用的结果，它促进二硼试剂的氧化，生成亲电子的双硼酸化物，在随后的氧化还原中性光催化C-H硼化反应中充当有效的硼化剂。

  DOI：

  10.1021/jacs.3c02185

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.
• Copper-Mediated Dehydrogenative C(sp³)–H Borylation of Alkanes
  作者：Ruocheng Sang、Wangyujing Han、Hanwen Zhang、Carla M. Saunders、Adam Noble、Varinder K. Aggarwal

  DOI：10.1021/jacs.3c02185

  日期：2023.7.19

  Borylations of inert carbon–hydrogen bonds are highly useful for transforming feedstock chemicals into versatile organoboron reagents. Catalysis of these reactions has historically relied on precious-metal complexes, which promote dehydrogenative borylations with diboron reagents under oxidant-free conditions. Recently, photoinduced radical-mediated borylations involving hydrogen atom transfer pathways

  惰性碳氢键的硼化对于将原料化学品转化为多功能有机硼试剂非常有用。这些反应的催化历来依赖于贵金属络合物，其在无氧化剂条件下促进二硼试剂的脱氢硼化反应。最近，涉及氢原子转移途径的光诱导自由基介导的硼基化已成为有吸引力的替代方案，因为它们提供了互补的区域选择性并在无金属条件下进行。然而，这些净氧化过程需要化学计量的氧化剂，因此无法与贵金属催化的对应物的高原子经济性竞争。在此，我们报道了 CuCl 2在无氧化剂条件下催化烷烃与双儿茶酚二硼的自由基介导的脱氢 C(sp 3 )–H 硼化反应。这是铜催化剂意想不到的双重作用的结果，它促进二硼试剂的氧化，生成亲电子的双硼酸化物，在随后的氧化还原中性光催化C-H硼化反应中充当有效的硼化剂。