diethyl 2-allyl-2-[(E)-4-bromo-2-butenyl]-1,3-propanedioate | 879098-77-8

• 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-allyl-2-[(E)-4-bromo-2-butenyl]-1,3-propanedioate
• 英文别名: diethyl 2-allyl-2-[4-bromo-2-butenyl]-1,3-propanedioate；6-bromo-4,4-di(ethoxycarbonyl)octa-1,6-diene；diethyl 2-[(E)-4-bromobut-2-enyl]-2-prop-2-enylpropanedioate
• CAS: 879098-77-8
• 化学式: C₁₄H₂₁BrO₄
• 分子量: 333.222
• InChiKey: RHUVYDJHEAFBGG-BQYQJAHWSA-N

物化性质

• 沸点：
  326.5±42.0 °C(Predicted)
• 密度：
  1.240±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  19
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 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-allyl-2-[(E)-4-bromo-2-butenyl]-1,3-propanedioate 在 sodium iodide 作用下， 以 丙酮 为溶剂， 反应 5.0h， 以96%的产率得到diethyl 2-allyl-2-[4-iodo-2-butenyl]-1,3-propanedioate
  参考文献：
  名称：

  Radical reactions initiated by the photochemical cleavage of carbon–indium bonds of organoindium compounds

  摘要：

  Intra- and intermolecular reactions of carbon-centered radicals generated by photolysis of organoindium compounds were examined. The photolysis of vinylindium compounds and indium acetylides provided vinyl and alkynyl radicals, respectively, which were trapped with ethyl iodoacetate giving the corresponding beta,gamma-unsaturated esters. Allylic indium compounds, prepared from 8-bromo- or 8-iodooct-1,6-dienes and powdered indium metal, underwent an intramolecular radical cyclization to afford the 5-exo-trig product. (c) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.01.013
• 作为产物：
  描述：

  烯丙基丙二酸二乙酯 、 1,4-二溴-2-丁烯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以47%的产率得到diethyl 2-allyl-2-[(E)-4-bromo-2-butenyl]-1,3-propanedioate
  参考文献：
  名称：

  Radical reactions initiated by the photochemical cleavage of carbon–indium bonds of organoindium compounds

  摘要：

  Intra- and intermolecular reactions of carbon-centered radicals generated by photolysis of organoindium compounds were examined. The photolysis of vinylindium compounds and indium acetylides provided vinyl and alkynyl radicals, respectively, which were trapped with ethyl iodoacetate giving the corresponding beta,gamma-unsaturated esters. Allylic indium compounds, prepared from 8-bromo- or 8-iodooct-1,6-dienes and powdered indium metal, underwent an intramolecular radical cyclization to afford the 5-exo-trig product. (c) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.01.013

文献信息

• Cobalt(diamine)-Catalyzed Cross-coupling Reaction of Alkyl Halides with Arylmagnesium Reagents:  Stereoselective Constructions of Arylated Asymmetric Carbons and Application to Total Synthesis of AH13205
  作者：Hirohisa Ohmiya、Hideki Yorimitsu、Koichiro Oshima

  DOI：10.1021/ja057560o

  日期：2006.2.1

  A cobalt-diamine complex catalyzes the cross-coupling reactions of primary and secondary alkyl halides with aryl Grignard reagents. It is confirmed that oxidative addition of alkyl halide to cobalt proceeds via a radical process. Optically pure Ueno-Stork halo acetals undergo diastereoselective cross-coupling reactions, the products of which are transformed into optically active THF derivatives. A

  钴-二胺配合物催化一级和二级烷基卤与芳基格氏试剂的交叉偶联反应。证实烷基卤化物与钴的氧化加成通过自由基过程进行。光学纯的 Ueno-Stork 卤代缩醛经历非对映选择性交叉偶联反应，其产物转化为光学活性的 THF 衍生物。在钴催化下的连续自由基环化/芳基化反应提供了极短的合成前列腺素 AH13205 途径。
• Preparation, Structure, and Reactivity of Nonstabilized Organoiron Compounds. Implications for Iron-Catalyzed Cross Coupling Reactions
  作者：Alois Fürstner、Rubén Martin、Helga Krause、Günter Seidel、Richard Goddard、Christian W. Lehmann

  DOI：10.1021/ja801466t

  日期：2008.7.1

  elimination reduce FeX n ( n = 2, 3) to clusters of the formal composition [Fe(MgX) 2] n . The behavior of these intermetallic species can be emulated by structurally well-defined lithium ferrate complexes of the type [Fe(C 2H 4) 4][Li(tmeda)] 2 ( 8), [Fe(cod) 2][Li(dme)] 2 ( 9), [CpFe(C 2H 4) 2][Li(tmeda)] ( 7), [CpFe(cod)][Li(dme)] ( 11), or [Cp*Fe(C 2H 4) 2][Li(tmeda)] ( 14). Such electron-rich

  提出了一系列前所未有的形式氧化态 -2、0、+1、+2 和 +3 的有机铁配合物，它们在很大程度上缺乏稳定配体，并且部分地也是电子不饱和的（14-、16-、 17 和 18 电子计数）。具体而言，结果表明，无法进行 β-氢化物消除的亲核试剂，如 MeLi、PhLi 或 PhMgBr，会迅速将 Fe(3+) 还原为 Fe(2+)，然后彻底烷基化金属中心。所得均质有机铁酸盐络合物 [(Me 4Fe)(MeLi)][Li(OEt 2)] 2 ( 3) 和 [Ph 4Fe][Li(Et 2O) 2][Li(1,4-二恶烷)] ( 5 ) 可以通过 X 射线晶体结构分析来表征。然而，这些异常敏感的化合物仅具有中等亲核性，仅将其有机配体转移到活化的亲电子试剂上，同时不能烷基化（杂）芳基卤化物，除非它们非常缺电子。形成鲜明对比的是，带有适合 β-氢化物消除的烷基残基的格氏试剂将 FeX n (n = 2
• Photochemical and radical initiator-induced reaction of allylic indium compounds
  作者：Tsunehisa Hirashita、Jiro Tanaka、Ayumi Hayashi、Shuki Araki

  DOI：10.1016/j.tetlet.2004.11.056

  日期：2005.1

  Intramolecular cyclization of allylic radicals generated from allylindium compounds both by photolysis or by the reaction of radical initiators was examined. The photolysis of allylic indium compounds, prepared from 8-bromo- or 8-iodooct-1,6-dienes and powdered indium metal, led to the formation of the 5-exo-trig products. Benzoyl peroxide as a radical initiator was also effective for the cyclization. In contrast

  研究了通过光解或自由基引发剂反应从烯丙基化合物生成的烯丙基自由基的分子内环化。由8-溴或8-碘辛基-1,6-二烯和粉状铟金属制得的烯丙基铟化合物的光解导致形成5- exo- trig产品。过氧化苯甲酰作为自由基引发剂对于环化也是有效的。相反，具有氧化性质的自由基引发剂，例如次氯酸叔丁酯，通过碘原子在铟原子上的氧化而诱导碘化，从而产生碘甲基环戊烷。
• Cross-Coupling of Alkyl Halides with Aryl Grignard Reagents Catalyzed by a Low-Valent Iron Complex
  作者：Rubén Martin、Alois Fürstner

  DOI：10.1002/anie.200460504

  日期：2004.7.26