4-methoxycyclohex-2-en-1-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methoxycyclohex-2-en-1-one
• 英文别名: 4-Methoxycyclohex-2-en-1-one
• 化学式: C₇H₁₀O₂
• 分子量: 126.155
• InChiKey: AWRPMEPPVWAWBZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  4-methoxycyclohex-2-en-1-one 在 ammonium acetate 、 sodium cyanoborohydride 、 三乙胺 作用下， 以 1,4-二氧六环 、 甲醇 、 二氯甲烷 为溶剂， 反应 34.0h， 生成 tert-butyl ((3aR*,4R*,7R*,7aS*)-2-benzyl-7-methoxyoctahydro-1H-isoindol-4-yl)carbamate
  参考文献：
  名称：

  发现和优化具有抗氟喹诺酮抗革兰氏阳性细菌活性的DNA促旋酶和拓扑异构酶IV抑制剂。

  摘要：

  本文中，我们描述了通过结合和稳定DNA裂解复合物抑制细菌DNA促旋酶和拓扑异构酶IV的新系列的发现和优化。该系列产品的优化导致化合物25的鉴定，该化合物对革兰氏阳性细菌具有强效活性，良好的体外安全性和出色的体内药代动力学特性。在小鼠大腿模型中，发现化合物25对氟喹诺酮敏感的金黄色葡萄球菌感染有效，其剂量低于莫西沙星。肺炎克雷伯菌的拓扑异构酶IV形成的三元复合物的X射线晶体结构，化合物25和切割的DNA表示该化合物不参与水-金属离子桥相互作用，也不与喹诺酮抗性确定区域（QRDR）中的残基形成直接接触。这表明与氟喹诺酮类药物相比，QRDR突变对25种抗菌活性的影响降低的结构基础。

  DOI：

  10.1021/acs.jmedchem.1c00375
• 作为产物：
  描述：

  4-羟基环己酮乙二醇缩醛 在 potassium tert-butylate 、 pyridinium hydrobromide perbromide 、 草酸 、 silica gel 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 4.5h， 生成 4-methoxycyclohex-2-en-1-one
  参考文献：
  名称：

  Stereospecific Retro-Diels-Alder fragmentation of stereoisomeric 3-methoxy- and 3,6-dialkoxytricyclo[6.2.2.02,7]dodeca-9-enes upon electron ionization

  摘要：

  The stereoisomeric 2,3-cis- and 2,3-trans-3-methoxytricyclo[6.2.2.0(2,7)]dodeca-9-enes endo-1 and exo-1 (endo and exo refer to the methoxy group) exhibit different behavior under electron ionization (EI): the m/z 80 cyclohexa-1,3-diene radical cation formed by retro-Diels-Alder (RDA) fragmentation is the most abundant ion in the 70 eV mass spectrum of endo-1, whereas exo-1 exhibits preferential formation of an m/z 111 ion corresponding to the O-methylcyclohex-2-en-1-one structure (ion a), which may be obtained by an RDA fragmentation accompanied by a hydrogen migration (RDA - H), with the charge retained in the dienophile moiety. A similar effect has been observed in the EI mass spectra of the four stereoisomeric 3-ethoxy-6-methoxytricyclo [6.2.2.0(2,7)] dodeca-9-enes 2; endo-2, with both endo-alkoxy groups, gives rise to the most abundant mit 80 ion via the regular RDA process, whereas the other three stereoisomers, with at least one exo-alkoxy group, afford the most abundant m/z 155 ions via the RDA -H process, which correspond to the 4-alkoxy-substituted analogues of the mit 111 ion a obtained from exo-1. Collision-induced dissociation measurements and a deuterium labeling study showed that che mit 155 ions obtained from the two trans-diethers (trans-2a and trans-2b) have isomeric structures b and c (a mixture of b and c is formed in the case of exo-2), and that the highly stereospecific RDA -H process involves a double hydrogen transfer, one from position 4 to the diene moiety and the other from position 3 to 4. The above stereospecific behavior shows that the thermodynamically favored RDA -H process has a higher activation energy than the regular RDA fragmentation in the case of endo-1 and endo-2. In all other isomers, which have at least one exo-alkoxyl, the activation energy of the KDA -H process is lower than that of RDA. The latter effect is ascribed to anchimeric assistance of the alkoxyl in the initial C-C bond cleavage in the stepwise RDA -H process, which is possible only when at least one alkoxyl has the exo configuration. (C) 1998 John Wiley & Sons, Ltd.

  DOI：

  10.1002/(sici)1096-9888(199803)33:3<229::aid-jms632>3.0.co;2-b

文献信息

• Ene Reductase Enabled Intramolecular β‐C−H Functionalization of Substituted Cyclohexanones for Efficient Synthesis of Bridged Bicyclic Nitrogen Scaffolds
  作者：Guangde Jiang、Chunshuai Huang、Wesley Harrison、Hongxiang Li、Megan Zhou、Huimin Zhao

  DOI：10.1002/anie.202302125

  日期：2023.5.22

  An unprecedented β-C−H functionalization reaction that is enabled by ene reductases is reported. When the reaction is coupled with photocatalysis, various 6-azabicyclo[3.2.1]octan-3-ones can be synthesized in a straightforward manner from readily available cyclohexenones and N-phenylglycines. This chemoenzymatic reaction can be carried out on a gram scale, and the product can be further selectively

  据报道，烯还原酶引发了前所未有的 β-C−H 功能化反应。当该反应与光催化结合时，可以从容易获得的环己烯酮和N-苯基甘氨酸以直接的方式合成各种6-氮杂双环[3.2.1]辛烷-3-酮。这种化学酶促反应可以在克级进行，并且产物可以进一步选择性衍生化。
• Tungsten-Catalyzed Heterocycloisomerization Approach to 4,5-Dihydro-benzo[<i>b</i>]furans and -indoles
  作者：Ethan L. Fisher、Sidney M. Wilkerson-Hill、Richmond Sarpong

  DOI：10.1021/ja3045647

  日期：2012.6.20

  A W(CO)(5).THF-catalyzed cycloisomerization of bicyclo[4.1.0] substrates to afford mono C4-substituted 4,5-dihydro-benzo[b]furans and -indoles is reported. The title compounds are versatile intermediates that lead to a range of fused bicycles including the cores of various furan-, benzofuran-, and indole-containing natural products. In many cases, the functionalization of the dihydro-benzo[b]furans and -indoles is orthogonal to that of the corresponding benzofurans and indoles and, thus, offers complementary approaches for synthesis.
• METHODS OF IMPROVING PRODUCTION OF MORPHINAN ALKALOIDS AND DERIVATIVES
  申请人：Antheia, Inc.

  公开号：US20220162656A1

  公开（公告）日：2022-05-26

  Methods and systems are provided for producing codeinone within an engineered non-plant cell. The method comprises, within the engineered non-plant cell, producing a thebaine product. The method also comprises, within the engineered non-plant cell, contacting the thebaine product with an enzyme having thebaine 6-O-demethylase activity, thereby producing a neopinone product. Additionally, the method comprises, within the engineered non-plant cell, contacting the neopinone product with a neopinone isomerase, thereby producing a codeinone product.