(+)-头孢菌素E | 97344-04-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃类
• 中文名称: (+)-头孢菌素E
• 英文名称: (-)-cephalosporolide F
• 英文别名: (+)-cephalosporolide E；Cephalosporolide E；(3aS,5R,5'R,6aS)-5'-methylspiro[3,3a,6,6a-tetrahydrofuro[3,2-b]furan-5,2'-oxolane]-2-one
• CAS: 97344-04-2
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: XNJDUGALSDZUTA-CHIQAWFVSA-N

物化性质

• 沸点：
  365.4±42.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (+)-cephalosporolide B 在 三氟乙酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 8.0h， 以59%的产率得到(+)-头孢菌素E
  参考文献：
  名称：

  Cephalosporolide B Serving as a Versatile Synthetic Precursor: Asymmetric Biomimetic Total Syntheses of Cephalosporolides C, E, F, G, and (4-OMe-)G

  摘要：

  Cephalosporolide B (Ces-B) was efficiently synthesized and exploited for the first time as a versatile biomimetic synthetic precursor for the chemical syntheses of not only cephalosporolides C, G, and (4-OMe-) G via a challenging diastereoselective oxa-Michael addition but also the structurally unprecedented cephalosporolides E and F via a novel biomimetic ring-contraction rearrangement. These findings provide the first direct chemical evidence that Ces-B may be the true biosynthetic precursor of cephalosporolides.

  DOI：

  10.1021/ol402913m

文献信息

• Total Synthesis of (+)-Cephalosporolide E and (-)-Cephalosporolide F en route to Bassianolone
  作者：Rodney Fernandes、Arun Ingle

  DOI：10.1055/s-0029-1218538

  日期：2010.1

  A stereoselective synthesis of (+)-cephalosporolide E and (―)-cephalosporolide F en route to bassianolone is described. The key steps involve cross metathesis to get the desired β,γ-unsaturated ester, asymmetric dihydroxylation to install the β-hydroxy-γ-lactone moiety and spiroketalization. Although attempts to get free bassianolone failed, the first total synthesis of natural cephalosporolides E

  描述了 (+)-头孢菌素 E 和 (-)-头孢菌素 F 的立体选择性合成，用于制备bassianolone。关键步骤包括交叉复分解以获得所需的 β,γ-不饱和酯、不对称二羟基化以安装 β-羟基-γ-内酯部分和螺酮化。尽管获得游离bassianolone的尝试失败了，但天然头孢菌素E和F的首次全合成已通过九步完成，总产率分别为6.3%和3.5%。
• Enantioselective Synthesis of Spiroacetals via Silver(I)-Promoted Alkylation of Hemiacetals: Total Synthesis of Cephalosporolides E and F
  作者：Stanley Chang、Robert Britton

  DOI：10.1021/ol302694s

  日期：2012.12.7

  A silver(I)-promoted intramolecular hemiacetal alkylation has been developed that converts readily available keto-chlorodiols into functionalized spiroacetals containing 5,5-, 5,6-, and 5,7-membered ring systems. The efficiency of this process is demonstrated in a concise total synthesis of the fungal metabolites cephalosporolides E and F.

  已经开发了银（I）促进的分子内半缩醛烷基化，其将容易获得的酮-氯二醇转化为含有5,5-，5,6-和5,7-元环系统的官能化的螺缩醛。此过程的效率在真菌代谢产物头孢菌内酯E和F的简明全合成中得到了证明。
• Total synthesis of naturally occurring cephalosporolides E/F
  作者：Chandrababu Naidu Kona、C.V. Ramana

  DOI：10.1016/j.tet.2014.04.026

  日期：2014.6

  A modular total synthesis of cephalosporolides E/F featuring sequential epoxide–alkyne coupling and subsequent highly regioselective gold catalyzed alkynolcycloisomerization of the resulting alkynetetrol to construct the central spiroketal core has been documented.

  头孢菌素E / F的模块化全合成具有连续的环氧化物-炔烃偶联作用，以及随后的高度区域选择性金催化的炔酮环烷醇环异构化反应，从而构建了中央螺环核心。
• A convergent synthesis of the [4.4]-spiroacetal-γ-lactones cephalosporolides E and F
  作者：Margaret A. Brimble、Orla C. Finch、Amanda M. Heapy、John D. Fraser、Daniel P. Furkert、Patrick D. O’Connor

  DOI：10.1016/j.tet.2010.11.107

  日期：2011.2

  A short convergent synthesis of the fungal metabolites cephalosporolides E and F is reported. The key step makes use of a chelation-controlled Mukaiyama aldol reaction to access the key acyclic spiroacetal precursor with the required syn stereochemistry. (C) 2010 Elsevier Ltd. All rights reserved.
• Cephalosporolide B Serving as a Versatile Synthetic Precursor: Asymmetric Biomimetic Total Syntheses of Cephalosporolides C, E, F, G, and (4-OMe-)G
  作者：Liyan Song、Yuan Liu、Rongbiao Tong

  DOI：10.1021/ol402913m

  日期：2013.11.15

  Cephalosporolide B (Ces-B) was efficiently synthesized and exploited for the first time as a versatile biomimetic synthetic precursor for the chemical syntheses of not only cephalosporolides C, G, and (4-OMe-) G via a challenging diastereoselective oxa-Michael addition but also the structurally unprecedented cephalosporolides E and F via a novel biomimetic ring-contraction rearrangement. These findings provide the first direct chemical evidence that Ces-B may be the true biosynthetic precursor of cephalosporolides.