3-ethenyl-2-methyl-4,4-dimethoxycyclobutenone | 156266-44-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-ethenyl-2-methyl-4,4-dimethoxycyclobutenone
• 英文别名: 3-Ethenyl-4,4-dimethoxy-2-methylcyclobut-2-en-1-one
• CAS: 156266-44-3
• 化学式: C₉H₁₂O₃
• 分子量: 168.192
• InChiKey: FMVVRSJAKSDSGV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-ethenyl-2-methyl-4,4-dimethoxycyclobutenone 在 氢溴酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.08h， 生成 3-(2-Bromoethyl)-4-methyl-3-cyclobuten-1,2-dione
  参考文献：
  名称：

  Synthetic Utility of Alkenylcyclobutenedione Monoketals. Michael Additions and the Synthesis of a Natural Benzofuranosesquiterpenequinone

  摘要：

  A new synthetic route to highly substituted cyclobutenones is reported. This involves the 1,6-addition of both heteroatom- and carbon-based nucleophiles to 4,4-dimethoxy-3-ethenyl-2-methylcyclobuten-1-one (8) to give further functionalized cyclobutenedione monoketals. These ketals function as precursors to quinones as illustrated by the synthesis of the natural benzofuranosesquiterpene 23.

  DOI：

  10.1021/jo00091a013
• 作为产物：
  描述：

  乙烯基-锂 、 2-methyl-3,4,4-tris(methyloxy)-2-cyclobuten-1-one 在 三氟乙酸酐 作用下， 生成 3-ethenyl-2-methyl-4,4-dimethoxycyclobutenone
  参考文献：
  名称：

  Synthetic Utility of Alkenylcyclobutenedione Monoketals. Michael Additions and the Synthesis of a Natural Benzofuranosesquiterpenequinone

  摘要：

  A new synthetic route to highly substituted cyclobutenones is reported. This involves the 1,6-addition of both heteroatom- and carbon-based nucleophiles to 4,4-dimethoxy-3-ethenyl-2-methylcyclobuten-1-one (8) to give further functionalized cyclobutenedione monoketals. These ketals function as precursors to quinones as illustrated by the synthesis of the natural benzofuranosesquiterpene 23.

  DOI：

  10.1021/jo00091a013

文献信息

• Oxy-Cope Rearrangements of Bicyclo[3.2.0]heptenones. Synthesis of Bicyclo[4.2.1]non-1(4)-en-6-ones and Bicyclo[5.2.1]dec-1(10)-en-5-ones
  作者：Sharad K. Verma、Que H. Nguyen、James M. MacDougall、Everly B. Fleischer、Harold W. Moore

  DOI：10.1021/jo991765w

  日期：2000.6.1

  1]non-1(4)-en-6-ones and the latter to the first examples of bicyclo[5.2.1]dec-1(10)-en-5-ones, compounds having exceptionally strained bridgehead double bonds. The transformations are controlled by the 6-exo-methyl group in the starting material along with the substituent at position-1 (bridgehead) which force attack of the lithium reagent from the concave face of the starting material, thus allowing the cyclopentenyl

  6-异-甲基双环[3.2.0]庚-7-酮及其2-亚烷基类似物可容易地由二烷基二烷基酯制备。这些化合物在用乙烯基锂处理后会发生面部氧-Cope环膨胀；前者导致双环[4.2。1] non-1（4）-en-6-ones和后者为双环[5.2.1] dec-1（10）-en-5-ones的第一个实例，这些化合物具有异常应变的桥头双键。转化受起始材料中的6-外甲基以及位置1（桥头）上的取代基控制，该取代基迫使锂试剂从起始材料的凹面进攻，从而形成环戊烯基或亚烷基参加大型活动。
• Cyclobutenone-Based Syntheses of Polyquinanes and Bicyclo[6.3.0]undecanes by Tandem Anionic Oxy-Cope Reactions. Total Synthesis of (±)-Precapnelladiene
  作者：James M. MacDougall、Vincent J. Santora、Sharad K. Verma、Philip Turnbull、Cameron R. Hernandez、Harold W. Moore

  DOI：10.1021/jo980712w

  日期：1998.10.1

  by a transannular aldol reaction of the intermediate bicyclo[6.3.0]undecadienone 4. Additional functionality is introduced by alkylation of the enolate 3 resulting from the oxy-Cope rearrangement. Phosphorylation or triflation of enolate 3 provides an entry into the bicyclo[6.3.0]undecane ring system. An application of this new methodology is demonstrated by the total synthesis of the sesquiterpene natural

  将乙烯基锂衍生物加到二烷基方酸衍生的双环庚烯酮的羰基上，例如1a和6a，引发低温阴离子加速的氧-Cope重排，以通过中间双环的环戊醛羟醛反应提供聚喹烷[6.3.0]。十一碳烯酮4。通过由氧基-Cope重排产生的烯酸酯3的烷基化引入了附加的官能度。烯酸酯3的磷酸化或三氟甲基化提供了进入双环[6.3.0]十一烷环系统的入口。这种新方法的应用通过二异丙基方酸（10步，12％）的全合成倍半萜烯天然产物（+/-）-capcapellaelladiene得以证明。
• Rearrangements of Linear Triquinanes to the Angular Isomers
  作者：James M. MacDougall、Harold W. Moore

  DOI：10.1021/jo9907686

  日期：1999.10.1

  Warming substituted linear triquinanes in t-BuOK/t-BuOH resulted in their isomerization to the corresponding angularly fused isomers in good yield (59-84%). An alternate route employs a base-catalyzed intramolecular Michael addition of bicyclo[6.3.0]undecenediones, a class of compounds found to be readily-available from 1-alkenylbicyclo[3.2.0]hepten-7-ones via a "one-pot" sequence of reactions. This method is complementary to the isomerization reaction since it provides access to angular triquinanes not readily available from their linear isomers.
• Synthetic Utility of Alkenylcyclobutenedione Monoketals. Michael Additions and the Synthesis of a Natural Benzofuranosesquiterpenequinone
  作者：Hui Liu、Leah M. Gayo、Robert W. Sullivan、Angela Y. H. Choi、Harold W. Moore

  DOI：10.1021/jo00091a013

  日期：1994.6

  A new synthetic route to highly substituted cyclobutenones is reported. This involves the 1,6-addition of both heteroatom- and carbon-based nucleophiles to 4,4-dimethoxy-3-ethenyl-2-methylcyclobuten-1-one (8) to give further functionalized cyclobutenedione monoketals. These ketals function as precursors to quinones as illustrated by the synthesis of the natural benzofuranosesquiterpene 23.
• Santora, Vincent J.; Moore, Harold W., Journal of the American Chemical Society, 1995, vol. 117, # 32, p. 8486 - 8487
  作者：Santora, Vincent J.、Moore, Harold W.

  DOI：——

  日期：——