ethyl-1-methyl-2-oxocyclopentane-1-carboxylate | 172825-15-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl-1-methyl-2-oxocyclopentane-1-carboxylate
• 英文别名: ethyl-1-methyl-2-oxocyclopentan-1-carboxylat；1-Ethoxycarbonyl-1-methyl-cyclopentanon-(2)；Ethyl (1R)-1-methyl-2-oxocyclopentanecarboxylate；ethyl (1R)-1-methyl-2-oxocyclopentane-1-carboxylate
• CAS: 172825-15-9
• 化学式: C₉H₁₄O₃
• 分子量: 170.208
• InChiKey: UIZCVGDHOSROCR-SECBINFHSA-N

物化性质

• 沸点：
  232.0±33.0 °C(Predicted)
• 密度：
  1.078±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl-1-methyl-2-oxocyclopentane-1-carboxylate 在 氢氧化钾 、 potassium hydrogensulfate 、 magnesium 、 乙硫醇钠 作用下， 以 乙二醇二甲醚 、 乙醇 为溶剂， 反应 100.0h， 生成 (1R)-2-(2-hydroxy-5-methylphenyl)-1-methylcyclopent-2-ene-1-carboxylic acid lactone
  参考文献：
  名称：

  Bryophyte Constituents; 6: Synthesis of Herbertene-Derived Sesquiterpenes from Herberta adunca

  摘要：

  高效全合成法被描述为从Herberta adunca中获得的消旋倍半萜烯herbertenolide（2）、α-herbertenol（3）和β-herbertenol（4）。外消旋体-herbertenolide（[+]-2）由手性纯的（-）-乙基（1R）-1-甲基-2-氧代环戊烷羧酸乙酯（9）制备，该物质通过面包酵母还原乙基2-氧代环戊烷羧酸乙酯（19）获得。

  DOI：

  10.1055/s-1996-4309
• 作为产物：
  描述：

  1-甲基-2-氧代环戊烷-1-羧酸乙酯 以61%的产率得到ethyl-1-methyl-2-oxocyclopentane-1-carboxylate
  参考文献：
  名称：

  Chiral Synthesis via Organoboranes. 42. Selective Reductions. 57. Efficient Kinetic Resolution of Representative α-Tertiary Ketones with B-Chlorodiisopinocampheylborane

  摘要：

  Kinetic resolution of racemic alpha-tertiary ketones with 0.5-0.6 molar equiv of B-chlorodiisopinocampheylborane provides the product alcohols in very high diastereomeric and enantiomeric excess, with the unreacted ketone recovered in very high ee. For example, ethyl 1-methyl-8-oxocyclopentane- and -cyclohexanecarboxylates are partially reduced to recover the ketone in 91 greater than or equal to 99% ee and the product alcohols in up to 94% de, with >90% ee for the major diastereomer. Bicyclic ketones, such as 1-methyl- and 1-ethylnorcamphor, camphor, and camphenilone, are readily resolved to provide the ketone in 92 to greater than or equal to 99% ee, with the product alcohol recovered in high de and ee. Dihydrospiro[bicyclo[3.2.1]octane-2,2'(3'H)-furan]-3-one is resolved to provide the ketone in greater than or equal to 99% ee and the product alcohol in greater than or equal to 99% de. In all the cases studied, the R-isomer of the ketone is recovered when (d)Ipc(2)BCl is used for kinetic resolution, while (l)Ipc(2)BCl provides the S-ketone. Optimum conditions for obtaining the product alcohol, or the ketone, or both, in very high yields and ee have been established.

  DOI：

  10.1021/jo951206z

文献信息

• Targeting NF-κB p65 with a Helenalin Inspired Bis-electrophile
  作者：John C. Widen、Aaron M. Kempema、Peter W. Villalta、Daniel A. Harki

  DOI：10.1021/acschembio.6b00751

  日期：2017.1.20

  by covalent molecules. The natural product helenalin, a sesquiterpene lactone, has been previously shown to target Cys38 on p65 and ablate its DNA-binding ability. Using helenalin as inspiration, simplified helenalin analogues were designed, synthesized, and shown to inhibit induced canonical NF-κB signaling in cell culture. Moreover, two simplified helenalin probes were proficient at forming covalent

  规范的NF-κB信号传导途径是细胞炎症反应的介体，也是开发多种人类疾病疗法的靶标。尽管已知有大量化合物抑制激活途径中的上游蛋白，但该途径中最远的下游蛋白p50 / p65转录因子异二聚体对小分子抑制具有顽固性。鉴于许多上游蛋白在多种生化途径中的作用，靶向p50 / p65异二聚体提供了提高靶点特异性的机会。为此，p65蛋白在其DNA结合界面上存在两个非二硫键半胱氨酸，Cys38和Cys120，它们可被共价分子靶向。天然产物helenalin，倍半萜内酯，先前已显示出可将Cys38靶向p65并消除其DNA结合能力。利用海伦纳林作为灵感，设计，合成了简化的海伦纳林类似物，并显示了其在细胞培养物中抑制诱导的经典NF-κB信号传导的作用。此外，两个简化的海伦素探针擅长形成共价蛋白加合物，与重组p65上的Cys38结合，并靶向HeLa细胞中的p65，而不会参与经典的NF-κB信号蛋白IκBα，p50
• Synthesis and Neurotrophic Activity Studies of <i>Illicium</i> Sesquiterpene Natural Product Analogues
  作者：Johannes Richers、Alexander Pöthig、Eberhardt Herdtweck、Claudia Sippel、Felix Hausch、Konrad Tiefenbacher

  DOI：10.1002/chem.201605362

  日期：2017.3.2

  the carbon framework of (±)‐Merrilactone A and (±)‐Anislactone A/B on a gram scale. This has allowed access to a series of structural analogues by modification of the core structure, including variation of oxidation levels and alteration of functional groups. In total, 15 derivatives of the natural products have been synthesized and tested for their neurite outgrowth activities. Our studies indicate

  神经营养天然产物具有潜在的特权结构，可用于开发抗神经退行性疾病的治疗剂。但是，仅进行了很少的研究来研究常见的药效基序和结构-活性关系（SAR）。在这里，研究结构上更简单的the毛神经营养倍半萜类似物介绍了家庭。简洁的合成路线可实现以克为单位制备（±）‐Merrilactone A和（±）‐Anislactone A / B的碳骨架。这样就可以通过修改核心结构来获得一系列结构类似物，包括氧化水平的变化和官能团的变化。总共合成了15种天然产物的衍生物，并测试了它们的神经突向外生长活性。我们的研究表明，有希望的生物活性可以通过结构更简单的天然产物类似物保留，而这些类似物可以通过简单的合成途径获得。
• A New Synthesis of (−)-Frontalin, the Bark Beetle Pheromone
  作者：Yutaka Nishimura、Kenji Mori

  DOI：10.1002/(sici)1099-0690(199802)1998:2<233::aid-ejoc233>3.0.co;2-m

  日期：1998.2

  (−)-Frontalin [(1S,5R)-1,5-dimethyl-6,8-dioxabicyclo[3.2.1]- octane (1)] was synthesized from ethyl 2-oxocyclopentane-1-carboxylate (2) as the starting material. Baker′s yeast was used for the asymmetric reduction of 2 to 3. The S configuration at C-1 of 1 was generated by diastereoselective methylation of the dianion derived from 3 to give 4. The present process furnished about 10 g of 1 with enantiomeric

  (-)-Frontalin [(1S,5R)-1,5-二甲基-6,8-二氧杂双环[3.2.1]-辛烷 (1)] 是由 2-氧代环戊烷-1-羧酸乙酯 (2) 合成的起始材料。面包酵母用于不对称还原 2 到 3。1 的 C-1 处的 S 构型是通过衍生自 3 的二价阴离子的非对映选择性甲基化产生的，得到 4。本方法为约 10 g 的 1 提供对映异构体纯度 89.1% ee
• Chiral Synthesis via Organoboranes. 43. Selective Reductions. 58. Reagent-Controlled Diastereoselective Reduction of (+)- and <b>(</b><b>−</b><b>)-</b>α-Chiral Ketones with (+)- and (−)-<i>B</i>-Chlorodiisopinocampheylborane
  作者：P. Veeraraghavan Ramachandran、Guang-Ming Chen、Herbert C. Brown

  DOI：10.1021/jo951207r

  日期：1996.1.1

  Asymmetric reduction of (+)- and (-)-alpha-chiral ketones with (+)- and (-)-B-chlorodiisopinocampheylborane provides the product alcohols in very high diastereomeric excess, with the matched pairs providing >100:1 selectivity and the mismatched pairs showing 4:1-15:1 selectivity. The high selectivity achieved even in the mismatched pairs reveals the power of the reagent to control the stereochemical outcome. The rates of the reaction of the matched pairs are faster than those of the mismatched pairs, In all the cases studied thus far, the (-)-reagent ((d)Ipc(2)BCl) and (S)ketone or the (+)-reagent ((l)Ipc(2)BCl) and (R)-ketone constitute matched pairs and the (-)-reagent and (R)-ketone or the (+)-reagent and (S)-ketone constitute mismatched pairs, A possible mechanism for the reductions is discussed.
• Bryophyte Constituents; 6: Synthesis of Herbertene-Derived Sesquiterpenes from Herberta adunca
  作者：Theophil Eicher、Frank Servet、Andreas Speicher

  DOI：10.1055/s-1996-4309

  日期：1996.7

  Efficient total syntheses are described for the racemic sesquiterpenes herbertenolide (2), α-herbertenol (3) and β-herbertenol (4) from Herberta adunca. ent-Herbertenolide [(+)-2] was prepared from enantiopure (-)-ethyl (1R)-1-methyl-2-oxocyclopentanecarboxylate (9) obtained from ethyl 2-oxocyclopentanecarboxylate (19) via reduction with baker’s yeast.

  高效全合成法被描述为从Herberta adunca中获得的消旋倍半萜烯herbertenolide（2）、α-herbertenol（3）和β-herbertenol（4）。外消旋体-herbertenolide（[+]-2）由手性纯的（-）-乙基（1R）-1-甲基-2-氧代环戊烷羧酸乙酯（9）制备，该物质通过面包酵母还原乙基2-氧代环戊烷羧酸乙酯（19）获得。