(1RS,4RS)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-one | 76735-29-0

• 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: (1RS,4RS)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-one
• 英文别名: (+/-)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane-5-one；(+/-)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-one；(+/-)-3-oxo-1,8-cineole；3-oxo-1,8-cineole；5-ketocineole；(1RS,4RS)-3-ketocineole；(1S,4S)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-one
• CAS: 76735-29-0
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: RFXTXEOQEMTRHL-XCBNKYQSSA-N

物化性质

• 沸点：
  225.4±15.0 °C(Predicted)
• 密度：
  1.027±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1RS,4RS)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-one 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 1.0h， 生成 (1RS,4SR,5RS)-1,3,3-trimethyl-2-oxabicyclo<2.2.2>octan-5-ol
  参考文献：
  名称：

  The 3-Hydroxycineoles

  摘要：

  本研究提供了有关 3-hydroxycineoles 1 和 2 的数据，以便随时识别这些代谢物，并确定它们在混合物中的对映体过量。在一种合成方法中，在一个三级中心观察到了不寻常的 SN2 型反转。

  DOI：

  10.1071/ch05144
• 作为产物：
  描述：

  桉叶油醇 在 chromium(VI) oxide 、 乙酸酐 、 溶剂黄146 作用下， 反应 58.0h， 以30%的产率得到(1RS,4RS)-1,3,3-trimethyl-2-oxabicyclo[2.2.2]octan-5-one
  参考文献：
  名称：

  肉桂醛衍生物的除草活性

  摘要：

  精油及其成分具有作为生态可接受的农药的潜力，也可能具有新颖的作用方式。在这项工作中，制备了大多数桉树油中主要成分天然单萜1,8-cineole 3和1,4-cineole 4的羟基和酯衍生物，并针对一年生黑麦草（黑麦草）进行了芽前除草活性。和萝卜（萝卜）变种 Long Scarlet（Long Scarlet）在基于实验室的生物测定法中进行了研究。1,8-桉树脑，桉树油和所有衍生物对一年生黑麦草和萝卜均表现出剂量依赖性的除草活性，其中许多衍生物相对于1,8-桉树脑和高桉树脑的桉树油具有更好的除草活性。与它们相关的羟基-桉树脑和羧酸相比，未观察到桉树脑酯衍生物的活性增加。没有观察到桉树脑酯衍生物的羧酸部分的亲脂性与除草活性之间的关系。结果表明这些桉树脑衍生物可能是环境可接受的除草剂。

  DOI：

  10.1021/jf101827v

文献信息

• Non-heme iron catalysis in C C, C–H, and CH2 oxidation reactions. Oxidative transformations on terpenoids catalyzed by Fe(bpmen)(OTf)2
  作者：David Clemente-Tejeda、Alejandro López-Moreno、Francisco A. Bermejo

  DOI：10.1016/j.tet.2013.02.013

  日期：2013.4

  The oxidation of terpene olefins with hydrogen peroxide in the presence of the non-hemo catalyst 5a afforded mixtures of epoxides whose composition was dependent upon the oxidation protocol used in each case. With terpenoid enones, the mixtures obtained evolved from clean epoxidation of α-ionone 23 to the clean allylic oxidation of damascone 28 due to the progressive deactivation of the electron density

  在非血液催化剂5a的存在下用过氧化氢氧化萜烯，得到环氧化物的混合物，其组成取决于每种情况下使用的氧化方案。对于萜类烯酮，由于在该系列中存在的双键上的电子密度的逐渐失活，获得的混合物从α-紫罗兰酮23的纯环氧化演变成大马士革28的纯烯丙基氧化。 双环和三环萜类化合物的氧化提供了从环氧化到烯烃降解，亚甲基和亚甲基活化产物的氧化产物。可能最吸引人的结果是由三环醚45合成马格努斯内酯46，收率为88％，转化率为100％。
• Selective C(sp³ )−H Aerobic Oxidation Enabled by Decatungstate Photocatalysis in Flow
  作者：Gabriele Laudadio、Sebastian Govaerts、Ying Wang、Davide Ravelli、Hannes F. Koolman、Maurizio Fagnoni、Stevan W. Djuric、Timothy Noël

  DOI：10.1002/anie.201800818

  日期：2018.4.3

  A mild and selective C(sp3 )-H aerobic oxidation enabled by decatungstate photocatalysis has been developed. The reaction can be significantly improved in a microflow reactor enabling the safe use of oxygen and enhanced irradiation of the reaction mixture. Our method allows for the oxidation of both activated and unactivated C-H bonds (30 examples). The ability to selectively oxidize natural scaffolds

  已开发出一种轻度的，选择性的C（sp3）-H有氧氧化，其通过分解钨酸盐进行光催化作用。在微流反应器中可以显着改善反应，从而可以安全地使用氧气并增强反应混合物的辐照度。我们的方法允许激活和未激活的CH键都被氧化（30个示例）。选择性氧化天然支架如（-）-氨氧化物，醋酸孕烯醇酮，（+）-香紫苏内酯和青蒿素的能力证明了这种新方法的实用性。
• Experimental and theoretical insights into the formation of weak hydrogen bonds and H⋯H bonding interactions in the solid-state structure of two eucalyptol derivatives
  作者：Carolina E. Galvez、Oscar E. Piro、Gustavo A. Echeverría、Norma Lis Robles、José O. G. Lezama、Sankaran Venkatachalam Sankaran、Subbiah Thamotharan、Margarita B. Villecco、María del H. Loandos、Diego M. Gil

  DOI：10.1039/d2nj00428c

  日期：——

  C–H⋯O hydrogen bonds and H⋯H bonding interactions. These interactions have also been described and studied energetically using DFT calculations. The nature and strength of these intermolecular contacts have been rationalized by using several computational tools including molecular electrostatic potential (MEP) surfaces, natural bond orbital analysis (NBO), Bader's theory of atoms in molecules (QTAIM)

  两种桉树脑衍生物，即 1,3,3-trimethyl-2-oxabicycle[2.2.2]oct-5-yl acetate ( 4 ) 和 1,3,3-trimethyl-2-oxabicycle[2.2.2]oct-5 ,8-乙酸酯 ( 6 ) 已被合成和表征。它们的晶体结构已通过单晶 X 射线衍射方法解析，表明这两种化合物的分子构象是由桉树醇部分甲基的 H 原子与 O- 之间的分子内 C-H⋯O 键稳定的。乙酰氧基原子。此外，我们通过使用 Hirshfeld 表面分析及其相关的二维指纹图对稳定两种结构的晶体堆积的分子间相互作用进行了详细研究。分析表明化合物的固态结构4和6主要通过C-H⋯O氢键和H⋯H键相互作用来稳定。还使用 DFT 计算大力描述和研究了这些相互作用。这些分子间接触的性质和强度已通过使用多种计算工具进行了合理化，包括分子静电势 (MEP) 表面、自然键轨道分析 (NBO)、Bader
• In vivo and in vitro hydroxylation of cineole and camphor by cytochromes P450CYP101A1, CYP101B1 and N242A CYP176A1
  作者：Jeanette E. Stok、Emma A. Hall、Isobella S.J. Stone、Margaret C. Noble、Siew Hoon Wong、Stephen G. Bell、James J. De Voss

  DOI：10.1016/j.molcatb.2016.03.004

  日期：2016.6

  Cytochromes P450 (P450s) are valuable enzymes that can generate a range of useful compounds via biocatalytic oxidations that complement traditional synthetic chemistry. In this study three bacterial P450s, qP450(cam) (CYP101A1), CYP101B1 and the mutant N242A-P450(cin) (N242A-CYP176A1), were used to produce a range of products from the oxidation of the monoterpenes (1R)- and (1S) -camphor and 1,8-cineole. We demonstrate that both in vitro and in vivo catalytic turnover with these P450s can produce a complement of up to seven hydroxycamphors and seven hydroxycineoles, in addition to compounds produced from further oxidation. The CYP101B1 whole cell catalytic system was found to produce 300-600 mg/L of culture of oxidation products that could be easily separated chromatographically. The CYP101B1 in vitro oxidation of 1,8-cineole primarily produced (1S)-5 alpha-hydroxycineole, which was 78% of the total product formed. However, the amount of (1S)-5a-hydroxycineole was reduced to 42% of the total products when isolated from the CYP101B1 whole cell system. (1S)-6 alpha-Hydroxycineole (96% ee) could be isolated from a whole cell catalytic turnover of 1,8-cineole by N242A-P450c,n in a yield of 46 mg/L (98% of the total product). However, the amount of product isolated ((1R)-5-endo-hydroxycamphor, 75% of the total products) from the whole cell catalytic oxidation of (1R) -camphor with N242A-P450c,n was much lower (6 mg/L) due to the inefficient use of reducing equivalents (3.5 + 0.5%) for substrate oxidation. These compounds will assist in the identification of specific structures in mechanistic investigations and structure elucidation, but further optimisation is required to generate larger quantities for synthetic applications. (C) 2016 Elsevier B.V. All rights reserved.
• 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.