5-ethyl-3-methyldihydrofuran-2(3H)-one

• 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: 5-ethyl-3-methyldihydrofuran-2(3H)-one
• 英文别名: cis-2-methylhexan-4-olide；(3S,5R)-5-ethyl-3-methyloxolan-2-one
• 化学式: C₇H₁₂O₂
• 分子量: 128.171
• InChiKey: YTALMPUNNICJOM-NTSWFWBYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  5-ethyl-3-methyldihydrofuran-2(3H)-one 在 2,6-二甲基吡啶 、 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 草酰氯 、 L-(+)-酒石酸二异丙酯 、 四丁基氟化铵 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 10.08h， 生成 (E)-ethyl 3-((2S,3S)-3-((2S,4R)-4-acetoxyhexan-2-yl)-2-methyloxiran-2-yl)acrylate
  参考文献：
  名称：

  曲线型AE的全合成和绝对构型

  摘要：

  描述了从内生真菌基因弯曲菌（Curvularia geniculata）的培养液中分离出的弯曲菌素A–E的第一个全合成。本文报道的不同的总合成方法证实了弯孢菌素A–E的绝对构型，并支持这些天然产物可能是通过一条通用的生物合成途径获得的。合成中涉及的关键步骤是外-亚甲基-γ-丁内酯的非对映选择性加氢成α-甲基-γ-丁内酯，Sharpless动力学拆分，Sharpless不对称环氧化以及分子内和分子间环氧化物开口。

  DOI：

  10.1021/jo301264k
• 作为产物：
  描述：

  3-methylene-5-vinyldihydrofuran-2(3H)-one 在 palladium 10% on activated carbon 、 氢气 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 5-ethyl-3-methyldihydrofuran-2(3H)-one
  参考文献：
  名称：

  曲线型AE的全合成和绝对构型

  摘要：

  描述了从内生真菌基因弯曲菌（Curvularia geniculata）的培养液中分离出的弯曲菌素A–E的第一个全合成。本文报道的不同的总合成方法证实了弯孢菌素A–E的绝对构型，并支持这些天然产物可能是通过一条通用的生物合成途径获得的。合成中涉及的关键步骤是外-亚甲基-γ-丁内酯的非对映选择性加氢成α-甲基-γ-丁内酯，Sharpless动力学拆分，Sharpless不对称环氧化以及分子内和分子间环氧化物开口。

  DOI：

  10.1021/jo301264k

文献信息

• Enantioselective Synthesis of α-<i>exo</i>-Methylene γ-Butyrolactones via Chromium Catalysis
  作者：Weiqiang Chen、Qin Yang、Tian Zhou、Qingshan Tian、Guozhu Zhang

  DOI：10.1021/acs.orglett.5b02597

  日期：2015.11.6

  obtained via a two-step sequence consisting of a highly enantioselective chromium-catalyzed carbonyl 2-(alkoxycarbonyl)allylation and lactonization. A variety of functional groups are compatible under the mild reaction conditions. The synthetic utility of this methodology was demonstrated by two short derivatization transformations and the enantioselective synthesis of (+)-methylenolactocin.

  通过两步序列获得了对映体富集的α-外-亚甲基γ-丁内酯，该过程由高度对映体选择性的铬催化的羰基2-（烷氧基羰基）烯丙基化和内酯化组成。在温和的反应条件下，各种官能团是相容的。该方法的合成效用通过两次短暂的衍生化转化和（+）-甲基烯醇内酯的对映选择性合成得到证明。
• Algicidal lactones from the marine <i>Roseobacter</i> clade bacterium <i>Ruegeria pomeroyi</i>
  作者：Ramona Riclea、Julia Gleitzmann、Hilke Bruns、Corina Junker、Barbara Schulz、Jeroen S Dickschat

  DOI：10.3762/bjoc.8.106

  日期：——

  Volatiles released by the marine Roseobacter clade bacterium Rugeria pomeroyi were collected by use of a closed-loop stripping headspace apparatus (CLSA) and analysed by GC–MS. Several lactones were found for which structural proposals were derived from their mass spectra and unambiguously verified by the synthesis of reference compounds. An enantioselective synthesis of two exemplary lactones was performed to establish the enantiomeric compositions of the natural products by enantioselective GC–MS analyses. The lactones were subjected to biotests to investigate their activity against several bacteria, fungi, and algae. A specific algicidal activity was observed that may be important in the interaction between the bacteria and their algal hosts in fading algal blooms.

  通过使用闭环吸附顶空装置（CLSA）收集了由海洋Roseobacter类细菌Rugeria pomeroyi释放的挥发性物质，并通过GC-MS进行了分析。发现了几种内酯，根据它们的质谱推导出了结构建议，并通过合成参考化合物进行了明确验证。进行了两种示范性内酯的对映选择性合成，以通过对映选择性GC-MS分析确定天然产物的对映构成。将内酯进行生物测试，以研究其对几种细菌、真菌和藻类的活性。观察到了特定的杀藻活性，这可能在细菌与藻类寄主之间的相互作用中起重要作用，尤其是在褪色藻类水华中。
• Case Study of a γ-Butyrolactone Alkylation with 1,3-Dimethyl-2-imidazolidinone as a Promoter
  作者：Bryan Li、Richard A. Buzon、Michael J. Castaldi

  DOI：10.1021/op010224h

  日期：2001.11.1

  1,3-Dimethyl 2-imidazolidinone (DMI) is of lower toxicological risk than 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU), hexamethyl-phosphorus triamide (HMPT), and hexamethylphosphoramide (HMPA). Formation of dialkylation byproducts is a common problem in lactone alkylation. DMI, used in stoichiometric amount, increases the rate of alkylation of gamma -butyrolactone 1 by >30-fold, therefore minimizing the dialkylation in multi-kilogram preparations. The isolated yield of the monoalkylated product 2 is >90%. The reaction protocol is also demonstrated to work on other lactone substrates and alkylating agents.
• [EN] CATALYST-CONTROLLED ALIPHATIC C-H OXIDATIONS<br/>[FR] OXYDATIONS D'UNE LIAISON C-H ALIPHATIQUE RÉGULÉES PAR CATALYSEUR
  申请人：UNIV ILLINOIS

  公开号：WO2015035412A1

  公开（公告）日：2015-03-12

  The invention provides simple small molecule, non-heme iron catalyst systems with broad substrate scope that can predictably enhance or overturn a substrate's inherent reactivity preference for sp3-hybridized C-H bond oxidation. The invention also provides methods for selective aliphatic C-H bond oxidation. Furthermore, a structure-based catalyst reactivity model is disclosed that quantitatively correlates the innate physical properties of the substrate to the site-selectivities observed as a function of the catalyst. The catalyst systems can be used in combination with oxidants such as hydrogen peroxide to effect highly selective oxidations of unactivated sp3 C-H bonds over a broad range of substrates.