2-甲氧基环戊-2-烯-1-酮 | 22323-97-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-甲氧基环戊-2-烯-1-酮
• 英文名称: 2-methoxycyclopent-2-en-1-one
• CAS: 22323-97-3
• 化学式: C₆H₈O₂
• 分子量: 112.128
• InChiKey: ZZPUYKVNYPHISS-UHFFFAOYSA-N

物化性质

• 沸点：
  107-109 °C(Press: 14 Torr)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  2-甲氧基环戊-2-烯-1-酮 在 N-溴代丁二酰亚胺(NBS) 、 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile 作用下， 以 乙腈 为溶剂， 反应 11.83h， 生成 (+/-)-1-methoxy-cis-bicyclo<3.2.0>hepta-3,6-dien-2-one
  参考文献：
  名称：

  Cavazza, Marino; Pietra, Francesco, Journal of the Chemical Society. Perkin transactions I, 1985, p. 2283 - 2288

  摘要：

  DOI：
• 作为产物：
  描述：

  3-Bromo-2-methoxycyclopentan-1-one 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 2-甲氧基环戊-2-烯-1-酮
  参考文献：
  名称：

  Fischer, Hans; Klippe, Michael; Lerche, Holger, Chemische Berichte, 1990, vol. 123, # 2, p. 399 - 404

  摘要：

  DOI：

文献信息

• 1,2- versus 1,4-Addition to α-donor-cyclopenten-1-ones; a comparison of calculated and experimental data †
  作者：Hanna S. H. Gautun、Rolf Carlson、Per N. Skancke

  DOI：10.1039/a905444h

  日期：——

  A series of α-donor-cyclopenten-1-ones, 1 (α-donor; X = H, Cl, Br, OMe, pyrrolidin-1-yl, SPh and SePh) were treated with methyllithium, lithium dimethylcuprate and cyanomethyllithium in tetrahydrofuran at –78 °C. The reactions between 1 and methyllithium gave 1,2-adducts in 28–75% yield. No trace of the corresponding 1,4-adduct was observed. By treatment of 1 with lithium dimethylcuprate only 1,4-addition was obtained in 51–76% yield, except for X = OMe or pyrrolidin-1-yl, which gave no reaction at all. In the reactions between 1 and cyanomethyllithium the 1,2-adducts were the main products (43–60%), but varying amounts of 1,4-adducts (8–30%) were also formed. The products formed have been fully characterized. Net atomic charges obtained by density functional theory (DFT) calculations of the lithiated cations of 1 with X = H, Cl, Br or OMe showed very small differences between the substituted and unsubstituted systems for all X, except for X = OMe. In this case the C2 position was positive rather than negative. The C3 position was found to be significantly more negative. The calculated relative energies of the methylated and cyanomethylated 1,2- and 1,4-adducts with X = H, Cl, Br and OMe indicated that the 1,4-adducts were thermodynamically favoured by 8 to 12 kcal mol–1 for all but one case. In the cyanomethylation of 1 with X = OMe the 1,2-adduct was predicted to be favoured by 12 kcal mol–1. Thus, the predominance of 1,2-attack in the reactions involving methyllithium and cyanomethyllithium cannot be explained by the relative thermodynamic stabilities of the products.

  一系列α-给体-环戊烯-1-酮，1（α-给体；X = H、Cl、Br、OMe、吡咯烷-1-基、SPh和SePh）在-78°C下与甲基锂、二甲基铜锂和氰基甲基锂在四氢呋喃中进行反应。1与甲基锂的反应生成1,2-加合物，产率为28-75%。未观察到相应的1,4-加合物。1与二甲基铜锂的反应仅得到1,4-加成产物，产率为51-76%，除了X = OMe或吡咯烷-1-基，这些情况下根本不发生反应。1与氰基甲基锂的反应中，1,2-加合物是主要产物（43-60%），但也形成了不同数量的1,4-加合物（8-30%）。形成的产物已完全表征。通过密度泛函理论（DFT）计算得到的1的锂化阳离子（X = H、Cl、Br或OMe）的净原子电荷显示，所有X的取代和未取代体系之间的差异非常小，除了X = OMe的情况。在这种情况下，C2位置是正的而不是负的。C3位置显著更加负电。计算得到的甲基化和氰基甲基化的1,2-和1,4-加合物（X = H、Cl、Br和OMe）的相对能量表明，除了一个情况外，1,4-加合物在热力学上更优，优于8到12 kcal/mol。在X = OMe的1的氰基甲基化中，预测1,2-加合物更优，优于12 kcal/mol。因此，涉及甲基锂和氰基甲基锂的反应中1,2-攻击的主导地位不能通过产物的相对热力学稳定性来解释。
• Asymmetric Bioreduction of Alkenes Using Ene–Reductases YersER and KYE1 and Effects of Organic Solvents
  作者：Yanto Yanto、Christoph K. Winkler、Stephanie Lohr、Mélanie Hall、Kurt Faber、Andreas S. Bommarius

  DOI：10.1021/ol200394p

  日期：2011.5.20

  activated alkenes by KYE1 from Kluyveromyces lactis and Yers-ER from Yersinia bercovieri, two ene–reductases from the Old Yellow Enzyme family, showed a broad substrate spectrum with a moderate to excellent degree of stereoselectivity. Both substrate- and enzyme-based stereocontrols were observed to furnish opposite stereoisomeric products. The effects of organic solvents on enzyme activity and stereoselectivity

  乳酸克鲁维酵母（Kluyveromyces lactis）的KYE1和伯氏耶尔森氏菌（Yersinia bercovieri）的耶尔-ER（Yersinia bercovieri）的耶尔-ER（Kye1）的不对称反式生物还原，显示了较宽的底物谱，具有中等至极好的立体选择性。观察到基于底物和基于酶的立体对照均提供相反的立体异构产物。这项研究概述了有机溶剂对酶活性和立体选择性的影响，其中显示了即使在高有机溶剂含量下，两相系统己烷和甲苯也能维持生物还原效率。
• Anhydrous Iron(III) Chloride Dispersed on Silica Gel; III.^1,2A Convenient and Mild Reagent for Deacetalization in Dry Medium
  作者：Antoine Fadel、Ramdane Yefsah、Jacques Salaün

  DOI：10.1055/s-1987-27833

  日期：——

  Acetals of various structures are conveniently cleaved under mild conditions by anhydrous iron(III) chloride dispersed silica gel in the absence of any solvent.

  在无任何溶剂的温和条件下，各种结构的缩醛可通过分散在硅胶上的无水三氯化铁便捷地裂解。
• Oxidative Alkoxylation/Dehydrogenation of Unactivated Cyclic Ketones with Simple Alcohols: Direct Route to α‐Alkoxy Cycloenones
  作者：Yizhe Yan、Shaoqing Li、Jianyong Wang

  DOI：10.1002/ejoc.202001140

  日期：2020.11.8

  An oxidative functionalization of cyclopentanones or cyclohexanones with simple alcohols was first demonstrated, affording a series of 2‐alkoxycyclopent‐2‐en‐1‐ones or 2‐alkoxycyclohex‐2‐en‐1‐ones in moderate to excellent yields.

  首次证明了使用简单的醇对环戊酮或环己酮的氧化功能化，可提供中等收率至优异收率的一系列2-烷氧基环戊-2-烯-1-酮或2-烷氧基环己-2-烯-1-酮。
• Asymmetric Synthesis of O-Protected Acyloins Using Enoate Reductases: Stereochemical Control through Protecting Group Modification
  作者：Christoph K. Winkler、Clemens Stueckler、Nicole J. Mueller、Desiree Pressnitz、Kurt Faber

  DOI：10.1002/ejoc.201001042

  日期：2010.11

  O-Protected cyclic acyloins were obtained in nonracemic form through asymmetric bioreduction of α,β-unsaturated alkoxy ketones by using 11 different enoate reductases from the "Old Yellow Enzyme" family. The stereochemical outcome of the biotransformation could be switched by variation of the O-protecting group or by the ring size of the substrate, which allows access to both stereoisomers in up to

  通过使用来自“老黄酶”家族的 11 种不同烯酸还原酶对 α,β-不饱和烷氧基酮进行不对称生物还原，以非外消旋形式获得 O-保护的环状 acyloins。生物转化的立体化学结果可以通过 O-保护基团的变化或底物的环大小来切换，这允许以高达 97% ee 的比例获得两种立体异构体，而 α-烷氧基烯酮很容易被接受为底物， β-类似物未转化。总的来说，α-烷氧基烯酮代表了一种新型的黄素依赖性烯还原酶底物。