4-methyl-2-oxobutyrolactone | 1944-45-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 4-methyl-2-oxobutyrolactone
• 英文别名: 5-Methyloxolane-2,3-dione
• CAS: 1944-45-2
• 化学式: C₅H₆O₃
• 分子量: 114.101
• InChiKey: NVZISLHGQBFBLS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  4-methyl-2-oxobutyrolactone 生成 巴豆醛
  参考文献：
  名称：

  在对位酮γ中，化石中的α-化合-γ-拉托尼对立的分解白蚁α-化合-γ-拉托尼对构成成分的分解

  摘要：

  A. Durch Kondensation von Na-oxalessigester mit n-Butyraldehyd andÖnanthaldehydund nachfolgende Ketonspaltung wurdenγ-n-Propyl-andγ-n​​-Hexyl-α-keto-γ-lactonherltellt。

  DOI：

  10.1002/hlca.19480310711
• 作为产物：
  描述：

  Α-亚甲基-Γ-戊内酯 在 臭氧 、 氧气 、 二甲基硫 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 4-methyl-2-oxobutyrolactone
  参考文献：
  名称：

  amphirionin 4的两种对映异构体的总合成：基于化学酶的功能化四氢呋喃策略。

  摘要：

  （-）-amphirionin-4和（+）-amphirionin-4的总合成以收敛和对映选择性的方式实现。通过消旋外消旋顺式-3-羟基-5-甲基二氢呋喃-2（3H）-one的旋光形式，构建了光学活性形式的amphirionin-4的四氢呋喃醇核心。使用Stille偶联有效地合成了多烯侧链。远程的C8立体中心是使用Nozaki-Hiyama-Kishi偶联反应构建的。对（-）-amphirionin-4和（+）-amphirionin-4的Mosher酯进行了详细的1H-NMR研究，以支持amphirionin-4的C-4和C-8不对称中心的绝对构型的分配。

  DOI：

  10.1016/j.tet.2017.02.031

文献信息

• Alcuni ?-cheto-?-lattoni con sostituenti alchilici in posizione ?
  作者：A. Rossi、H. Schinz

  DOI：10.1002/hlca.19480310226

  日期：——

  Durch Kondensation von Natrium-oxalessigester rnit aliphatischen Aldehyden gelangt man xu α-Keto-β-carboxathyl-γ-alkyl-γ-lactonen (A)

  草酰乙酸钠与脂肪族醛的缩合导致生成xα-酮基-β-羧基-γ-烷基-γ-内酯（A）
• Gas phase synthesis of methylene lactones using catalysts derived from hydrotalcite precursors
  申请人：Manzer Ernest Leo

  公开号：US20060084818A1

  公开（公告）日：2006-04-20

  Process for converting certain lactones to their alpha-methylene substituted forms using (i) a catalyst derived from a hydrotalcite or (ii) a composite catalyst comprising the hydrotalcite-derived catalyst into which at least one of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium has been incorporated.

  将某些内酯转化为其α-亚甲基取代形式的过程，使用(i)源自水滑石的催化剂，或者(ii)由水滑石衍生的催化剂组成的复合催化剂，其中至少其中之一的锂、钠、钾、铷、铯、镁、钙、锶、钡已被合并进去。
• Design of substituted tetrahydrofuran derivatives for HIV-1 protease inhibitors: synthesis, biological evaluation, and X-ray structural studies
  作者：Arun K. Ghosh、Daniel Lee、Ashish Sharma、Megan E. Johnson、Ajay K. Ghosh、Yuan-Fang Wang、Johnson Agniswamy、Masayuki Amano、Shin-ichiro Hattori、Irene T. Weber、Hiroaki Mitsuya

  DOI：10.1039/d4ob00506f

  日期：——

  Substituted tetrahydrofuran derivatives were designed and synthesized to serve as the P2 ligand for a series of potent HIV-1 protease inhibitors. Both enantiomers of the tetrahydrofuran derivatives were synthesized stereoselectivity in optically active forms using lipase-PS catalyzed enzymatic resolution as the key step. These tetrahydrofuran derivatives are designed to promote hydrogen bonding and van der

  设计并合成了取代的四氢呋喃衍生物作为一系列有效的 HIV-1 蛋白酶抑制剂的 P2 配体。以脂肪酶-PS 催化的酶拆分为关键步骤，以光学活性形式立体选择性地合成了四氢呋喃衍生物的两种对映体。这些四氢呋喃衍生物旨在促进与 HIV-1 蛋白酶活性位点 S2 亚位点主链原子之间的氢键作用和范德华相互作用。几种抑制剂表现出非常有效的 HIV-1 蛋白酶抑制活性。抑制剂结合的 HIV-1 蛋白酶的高分辨率 X 射线晶体结构为了解活性位点中的配体结合位点相互作用提供了重要的见解。
• Comparison of Two Metal-Dependent Pyruvate Aldolases Related by Convergent Evolution: Substrate Specificity, Kinetic Mechanism, and Substrate Channeling
  作者：Weijun Wang、Perrin Baker、Stephen Y. K. Seah

  DOI：10.1021/bi100251u

  日期：2010.5.4

  HpaI and BphI are two pyruvate class II aldolases found in aromatic meta-cleavage degradation pathways that catalyze similar reactions but are not related in sequence. Steady-state kinetic analysis of the aldol addition reactions and product inhibition assays showed that HpaI exhibits a rapid equilibrium random order mechanism while BphI exhibits a compulsory order mechanism, with pyruvate binding first. Both aldolases are able to utilize aldehyde acceptors two to five carbons in length; however, HpaI showed broader specificity and had a preference for aldehydes containing longer linear alkyl chains or C2-OH substitutions. Both enzymes were able to bind 2-keto acids larger than pyruvate, but only HpaI was able to utilize both pyruvate and 2-ketobutanoate as carbonyl donors in the aldol addition reaction. HpaI lacks stereospecific control producing racemic mixtures of 4-hydroxy-2-oxopentanoate (HOPA) from pyruvate and acetaldehyde while BphI synthesizes only (4S)-HOPA. BphI is also able to utilize acetaldehyde produced by the reduction of acetyl-CoA catalyzed by the associated aldehyde dehydrogenase, BphJ. This aldehyde was directly channeled from the dehydrogenase to the aldolase active sites, with an efficiency of 84%. Furthermore, the BphJ reductive deacylation reaction increased 4-fold when BphI was catalyzing the aldol addition reaction. Therefore, the BphI-BphJ enzyme complex exhibits unique bidirectionality in substrate channeling and allosteric activation.
• Mechanism of the dehydrogenase reaction of DmpFG and analysis of inter-subunit channeling efficiency and thermodynamic parameters in the overall reaction
  作者：Natalie E. Smith、Wan Jun Tie、Gavin R. Flematti、Keith A. Stubbs、Ben Corry、Paul V. Attwood、Alice Vrielink

  DOI：10.1016/j.biocel.2013.05.028

  日期：2013.8

  The bifunctional, microbial enzyme DmpFG is comprised of two subunits: the aldolase, DmpG, and the dehydrogenase, DmpF. DmpFG is of interest due to its ability to channel substrates between the two spatially distinct active sites. While the aldolase is well studied, significantly less is known about the dehydrogenase. Steady-state kinetic measurements of the reverse reaction of DmpF confirmed that the dehydrogenase uses a ping-pong mechanism, with substrate inhibition by acetyl CoA indicating that NAD(+)/NADH and CoA/acetyl CoA bind to the same site in DmpF. The Km of DmpF for exogenous acetaldehyde as a substrate was 23.7 mM, demonstrating the necessity for the channel to deliver acetaldehyde directly from the aldolase to the dehydrogenase active site. A channeling assay on the bifunctional enzyme gave an efficiency of 93% indicating that less than 10% of the toxic acetaldehyde leaks out of the channel into the bulk media, prior to reaching the dehydrogenaSe active site. The thermodynamic activation parameters of the reactions catalyzed by the aldolase, the dehydrogenase and the DmpFG complex were determined. The Gibb's free energy of activation for the dehydrogenase reaction was lower than that obtained for the full DmpFG reaction, in agreement with the high K-cat obtained for the dehydrogenase reaction in isolation. Furthermore, although both the DmpF and DmpG reactions occur with small, favorable entropies of activation, the full DmpFG reaction occurs with a negative entropy of activation. This supports the concept of allosteric structural communication between the two enzymes to coordinate their activities. (C) 2013 Elsevier Ltd. All rights reserved.