diethyl 2,3-butadien-1-yl-propargyl-malonate | 198695-22-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: diethyl 2,3-butadien-1-yl-propargyl-malonate
• CAS: 198695-22-6
• 化学式: C₁₄H₁₈O₄
• 分子量: 250.295
• InChiKey: MNROGELPEXXPMI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  18
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl 2,3-butadien-1-yl-propargyl-malonate 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 0.25h， 生成 Triethyl bicyclo[4.2.0]octa-1(8),5-diene-3,3,8-tricarboxylate
  参考文献：
  名称：

  微波辐射下烯丙炔的高效[2 + 2]分子内环化：稠合双环化合物的构建。

  摘要：

  1,6-和1,7-炔烃羧酸的钯[2 + 2]环加成反应以及各种1，n-炔烃的微波介导的[2 + 2]环加成反应，特别是微波照射的[2 + 2炔烃的环加成反应可提供一种简单，通用且环保的合成方法，以稠合双环[m，2,0]链二烯。

  DOI：

  10.1039/b508306k
• 作为产物：
  描述：

  2-(2-丙炔-1-基)丙二酸二乙酯 在 sodium hydride 、 二异丙胺 、 copper(I) bromide 作用下， 以 1,4-二氧六环 、 N,N-二甲基甲酰胺 为溶剂， 生成 diethyl 2,3-butadien-1-yl-propargyl-malonate
  参考文献：
  名称：

  微波辐射下烯丙炔的高效[2 + 2]分子内环化：稠合双环化合物的构建。

  摘要：

  1,6-和1,7-炔烃羧酸的钯[2 + 2]环加成反应以及各种1，n-炔烃的微波介导的[2 + 2]环加成反应，特别是微波照射的[2 + 2炔烃的环加成反应可提供一种简单，通用且环保的合成方法，以稠合双环[m，2,0]链二烯。

  DOI：

  10.1039/b508306k

文献信息

• Regio- and Stereochemical Control in Bis-functionalization−Cyclization:  Use of Alleneyne Precursors for Carbocyclic and Heterocyclic Synthesis
  作者：Seunghoon Shin、T. V. RajanBabu

  DOI：10.1021/ja011281t

  日期：2001.8.1
• Stereoselective Cyclization of Functionalized 1,<i>n</i>-Diynes Mediated by [X−Y] Reagents [X−Y = R₃Si−SnR′₃ or (R₂N)₂B−SnR′₃]: Synthesis and Properties of Atropisomeric 1,3-Dienes
  作者：Ramakrishna Reddy Singidi、Amanda M. Kutney、Judith C. Gallucci、T. V. RajanBabu

  DOI：10.1021/ja105939v

  日期：2010.9.22

  The borylstannane [-N(Me)CH2CH2(Me)N-]B-SnMe3 is a superior reagent capable of effecting bisfunctionalization-cyclization in several highly functionalized 1,n-diynes, 1,n-enynes, and 1,n-allenynes (including 1,2-dipropargylbenzenes, 2,2'-dipropargylbiphenyls, 4,5-dipropargyldioxolanes, and 1,4-dipropargyl-beta -lactams) where the more well-known silylstannanes fail. Variable-temperature NMR studies showed that conformational restraints imposed by selected backbones increase the activation barrier for the helical isomerization in (Z,2)-dienes that are generated in the cyclization of the diynes. In the biphenyl and dioxolane systems, the reactions proceed with surprisingly good regio- and stereoselectivity. The resulting diazaborolidine derivatives are hydrolytically unstable but can be isolated by recrystallization or precipitation. For further synthetic applications, it is advantageous to convert these compounds in situ into the corresponding dioxaborolidines with either retention of the Me3Sn group or replacement of this group via halodestannylation. The configurations of the vinyl moieties are preserved in these reactions. Highly functionalized dibenzocyclooctadienes, which adorn the carbon frames of several important cytotoxic natural products, can be synthesized using this chemistry.
• Cyclization of 1-Bromo-2,7- and 1-Bromo-2,8-Enynes Mediated by Indium
  作者：Phil Ho Lee、Sundae Kim、Kooyeon Lee、Dong Seomoon、Hyunseok Kim、Seokju Lee、Misook Kim、Mijeong Han、Kwanghyun Noh、Tom Livinghouse

  DOI：10.1021/ol048175r

  日期：2004.12.1

  [Graphics]The cyclization of 1-bromo-2,7- and 1-bromo-2,8-enynes mediated by indium in DMF produced five- and six-membered cyclic compounds. Although KI was a necessary additive in the cyclization of terminal 1-bromo-2,7-enynes to give the desired products at 25degreesC, reactions of terminal 1-bromo-2,8-enynes and internal 1-bromo-2,7-enynes with indium proceeded at 100degreesC in DMF without KI. After cyclizations, subsequent cross-coupling reaction and iodolysis increase the usefulness of this reaction.