3,4,4-trimethoxy-2-vinylcyclobut-2-en-1-one | 144790-82-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4,4-trimethoxy-2-vinylcyclobut-2-en-1-one
• 英文别名: 2-Ethenyl-3,4,4-trimethoxycyclobut-2-en-1-one
• CAS: 144790-82-9
• 化学式: C₉H₁₂O₄
• 分子量: 184.192
• InChiKey: ROOFDPDCAZLWRM-UHFFFAOYSA-N

物化性质

• 沸点：
  298.6±40.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,4,4-trimethoxy-2-vinylcyclobut-2-en-1-one 在 正丁基锂 、 三氟乙酸酐 作用下， 以 四氢呋喃 为溶剂， 生成 1-hydroxy-1,2-diethenyl-3-n-butyl-4,4-dimethoxy-2-cyclobutene
  参考文献：
  名称：

  A potentially general regiospecific synthesis of substituted quinones from dimethyl squarate

  摘要：

  A potentially general regiospecific synthesis of benzo- and naphthoquinones is described. This method starts with dimethyl squarate (1), which is converted to the cyclobutenone ketal 3 upon sequential treatment with an organolithium reagent and then BF3 etherate or TFAA in THF/methanol. Treatment of these with a second lithium reagent followed by hydrolysis gives the cyclobutenones 5. Addition of an alkynyl-, alkenyl- or aryllithium agent to 5 followed by hydrolysis of the ketal linkage gives the corresponding 4-alkynyl- 4-alkenyl- or 4-aryl-4-hydroxycyclobutenones 7-9, and these readily rearrange to the respective quinones or hydroquinones upon thermolysis in refluxing benzene. In a similar fashion, 15 was employed as a reagent to prepare mono- and disubstituted hydroquinones and quinones.

  DOI：

  10.1021/jo00051a040
• 作为产物：
  描述：

  甲醇 、 4-Ethenyl-4-hydroxy-2,3-dimethoxycyclobut-2-en-1-one 在 三氟化硼乙醚 作用下， 以 四氢呋喃 为溶剂， 以80%的产率得到3,4,4-trimethoxy-2-vinylcyclobut-2-en-1-one
  参考文献：
  名称：

  A potentially general regiospecific synthesis of substituted quinones from dimethyl squarate

  摘要：

  A potentially general regiospecific synthesis of benzo- and naphthoquinones is described. This method starts with dimethyl squarate (1), which is converted to the cyclobutenone ketal 3 upon sequential treatment with an organolithium reagent and then BF3 etherate or TFAA in THF/methanol. Treatment of these with a second lithium reagent followed by hydrolysis gives the cyclobutenones 5. Addition of an alkynyl-, alkenyl- or aryllithium agent to 5 followed by hydrolysis of the ketal linkage gives the corresponding 4-alkynyl- 4-alkenyl- or 4-aryl-4-hydroxycyclobutenones 7-9, and these readily rearrange to the respective quinones or hydroquinones upon thermolysis in refluxing benzene. In a similar fashion, 15 was employed as a reagent to prepare mono- and disubstituted hydroquinones and quinones.

  DOI：

  10.1021/jo00051a040

文献信息

• Toward the total synthesis of citreamicin η: Synthesis of the pentacyclic core and GAB-ring annelation model studies
  作者：Shawn Blumberg、Stephen F. Martin

  DOI：10.1016/j.tet.2018.04.049

  日期：2018.9

  di-tert-butylsilyl (DTBS) ethers to protect electron-rich benzyl alcohols toward ionization under acidic conditions. We also developed an improved protocol for selective o-bromination of phenols utilizing N-bromosuccinimide (NBS) and tetramethylguanidine (TMG) that promises to be generally useful. Finally, we developed a modular approach for the synthesis of isoquinolones and dihydro-5H-oxazolo[3,2-b]isoquinoline-2

  多环黄酮抗生素citreamicamicinη的五环核的短时11步合成已经完成。尽管基本方法是由我们先前对多环蒽酮化学的探索启发而来的，但本报告对摩尔重排有一些新见解，并对我们的原始方法进行了一些改进，包括将芳基锂添加到方酸酯中，将乙炔铈铈添加到受阻酮中。利用PDA作为内部指示剂，以及使用环状二叔丁基甲硅烷基（DTBS）醚保护富含电子的苄醇在酸性条件下不被电离。我们还开发了用于选择性的改进的协议ø利用酚的-bromination N-有望普遍使用的溴代琥珀酰亚胺（NBS）和四甲基胍（TMG）。最后，我们开发了一种用于合成异喹诺酮和二氢-5H-恶唑并[3,2 - b ]异喹啉-2,5（3H）-二酮的模块化方法，该方法具有烷氧基羰基化，丙酮芳基化，酰胺基转移的新序列。
• Total synthesis of the aglycone of IB-00208
  作者：Daniel Knueppel、Jingyue Yang、Bo Cheng、Douglas Mans、Stephen F. Martin

  DOI：10.1016/j.tet.2015.05.024

  日期：2015.9

  A total synthesis of the aglycone of IB-00208 was accomplished in 22 steps using a newly developed approach towards polycyclic 1,4-dioxygenated xanthones from benzocyclobutenones. The generality of this entry to xanthones was initially established on several model systems before it was successfully applied to the construction of the hexacyclic core of the natural product. A new and potentially general

  IB-00208糖苷配基的总合成使用新开发的方法从苯并环丁烯酮向多环1,4-二加氧的氧杂蒽开发，共分22个步骤完成。最初在几种模型系统上建立了氧杂蒽酮的通用性，然后才成功地将其用于天然产物的六环核的构建。还开发了一种使用闭环复分解（RCM）的有角度稠合苯并环丁烯酮的新方法，并且可能具有通用性。
• Approaches to Polycyclic 1,4-Dioxygenated Xanthones. Application to Total Synthesis of the Aglycone of IB-00208
  作者：Jingyue Yang、Daniel Knueppel、Bo Cheng、Douglas Mans、Stephen F. Martin

  DOI：10.1021/ol503336t

  日期：2015.1.2

  Hexacyclic xanthone natural products such as IB-00208 present a formidable challenge in organic synthesis. A new approach to polycyclic 1,4-dioxygenated xanthones from benzocyclobutenones has been developed and applied to the first total synthesis of the aglycone of IB-00208. The 22-step synthesis features an acetylide stitching process that joins an aryl aldehyde with an angularly fused benzocyclobutenone

  六环黄酮天然产物（如IB-00208）在有机合成中提出了严峻的挑战。已经开发了一种从苯并环丁烯酮生产多环1,4-二加氧氧杂蒽酮的新方法，并将其应用于IB-00208糖苷配基的首次全合成。该22步合成的特征在于乙炔键合工艺，该工艺将芳基醛与有角度稠合的苯并环丁烯酮连接在一起，该苯环丁烯酮是通过闭环易位反应制备的。所得的炔属苯并环丁烯酮二醇经过摩尔重排，得到中间体，该中间体进一步以对苯二酚-醌互变异构体的混合物形式被制备为IB-00208的糖苷配基。
• Synthesis of the Pentacyclic Core of Citreamicin η
  作者：Shawn Blumberg、Stephen F. Martin

  DOI：10.1021/acs.orglett.6b03760

  日期：2017.2.17

  polycyclic xanthone natural products that have not yet yielded to total synthesis. A concise 11-step synthesis of the pentacyclic core of citreamicin η is now reported that features the use of a general approach for the synthesis of 1,4-dioxygenated xanthones. The synthesis also showcases improved techniques for effecting regioselective bromination of certain substituted phenols and coupling of acetylides

  所述桔霉素包括尚未产生总合成的一类新的多环x吨酮天然产物。现在报道了一个简单的11步合成citreamicinη的五环核的方法，该方法具有使用合成1,4-二氧合氧杂蒽酮的通用方法的特点。该合成还展示了用于实现某些取代的苯酚的区域选择性溴化以及将乙炔化物与受阻酮偶联的改进技术。
• Synthesis of Angularly-Fused Benzocyclobutenedione Monoketals:  Useful Synthetic Intermediates to Angucyclines
  作者：Ralf Tiedemann、Matthew J. Heileman、Harold W. Moore、Ernst Schaumann

  DOI：10.1021/jo982422l

  日期：1999.4.1