Methoxycarbonyl-2 heptadiene-4,5 oate de methyle | 113495-69-5

• 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: Methoxycarbonyl-2 heptadiene-4,5 oate de methyle
• 英文别名: dimethyl penta-2,3-dien-1-ylmalonate；dimethyl 2-(penta-2,3-dienyl)malonate
• CAS: 113495-69-5
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: RZJGUJGWGKUUIW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  14
• 可旋转键数：
  6
• 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：

  Methoxycarbonyl-2 heptadiene-4,5 oate de methyle 在 sodium tetrahydroborate 、 C₃₀H₃₅F₁₂NOSi 、 sodium methylate 、 palladium diacetate 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  Dual Amine and Palladium Catalysis in Diastereo- and Enantioselective Allene Carbocyclization Reactions

  摘要：

  A pyrrolidine and Pd catalyzed diastereoselective carbocyclization of aldehyde and ketone-linked allenes has been developed. The cooperative organo/metal-catalyzed cyclization reaction, which presumably proceeds via an enamine intermediate, is efficient and broad in scope. Also, it has been extended to a catalytic asymmetric variant using diarylprolinol-based organocatalysts to afford substituted cyclopentane and pyrrolidine reaction products in up to 82% ee.

  DOI：

  10.1021/ol303128s
• 作为产物：
  描述：

  penta-2,3-dien-1-ol 在 sodium hydride 、 potassium hydroxide 作用下， 以 四氢呋喃 、 乙醚 、 mineral oil 为溶剂， 反应 4.0h， 生成 Methoxycarbonyl-2 heptadiene-4,5 oate de methyle
  参考文献：
  名称：

  Dual Amine and Palladium Catalysis in Diastereo- and Enantioselective Allene Carbocyclization Reactions

  摘要：

  A pyrrolidine and Pd catalyzed diastereoselective carbocyclization of aldehyde and ketone-linked allenes has been developed. The cooperative organo/metal-catalyzed cyclization reaction, which presumably proceeds via an enamine intermediate, is efficient and broad in scope. Also, it has been extended to a catalytic asymmetric variant using diarylprolinol-based organocatalysts to afford substituted cyclopentane and pyrrolidine reaction products in up to 82% ee.

  DOI：

  10.1021/ol303128s

文献信息

• Rhodium‐Catalyzed Dynamic Kinetic [4+2] Cycloaddition of Allene‐1,3‐Dienes
  作者：Yulin Han、Anni Qin、Qian Zhang、Xue Zhang、Hui Qian、Shengming Ma

  DOI：10.1002/anie.202211635

  日期：2022.11.21

  A rhodium/Malphos catalytic recipe has been developed for the dynamic kinetic intramolecular Diels–Alder cycloaddition of allene-1,3-dienes. The desired cis-fused [4.3.0]bicyclic products were obtained with decent yields and excellent stereo- and enantioselectivity. Its dynamic kinetic nature has been confirmed by careful mechanistic studies.

  已经开发了一种铑/Malphos 催化配方，用于丙二烯-1,3-二烯的动态动力学分子内 Diels-Alder 环加成。获得了所需的顺式稠合 [4.3.0] 双环产物，具有良好的收率和出色的立体选择性和对映选择性。其动态动力学性质已通过仔细的机理研究得到证实。
• Cobalt‐Catalyzed Intramolecular Cycloadditions of Alkenylidenecyclopropanes with Alkenes and Dienes
  作者：Eduardo da Concepción、Israel Fernández、José L. Mascareñas、Fernando López

  DOI：10.1002/adsc.202301040

  日期：2024.2.20

  applied to promote the cycloaddition of ACP 1 b, bearing a fully carbonade tether, which gave the desired bicarbocyclic adduct 2 b in 65% yield (Scheme 2). In consonance with the assumption that alkenes are more challenging partners than alkynes, substrates with substituted alkenes like 1 c–1 e (R’=Ph, Me or CO2Me) failed to give the expected cycloadducts. However, the cycloaddition of the bisalkylidenecyclopropane

  过渡金属催化 (TMC) 形式环加成是从简单无环材料构建多环产物的最实用、最通用的方法之一。1在迄今为止开发的不同环加成策略中，那些涉及应变碳环反应物中 C−C 键活化的策略特别有吸引力。2 在这方面，我们和其他人已经证明，容易获得的亚烷基环丙烷（ACP）可以在各种合成强大的（3+2）、（3+4）和（3+2+n）中充当通用的三碳组分。正式环加成。3, 4这些和其他 TMC 成环基于应变碳环的 C−C 活化，2通常需要具有贵金属过渡金属（如 Rh、Pd 或 Ir）的催化剂。地球上丰富的第一行过渡金属的使用将提供更可持续和更有吸引力的选择，但主要限于镍衍生物5以及基于铁和钴催化剂的一些例子。6, 7示例的稀缺很可能是由于控制催化循环的氧化还原步骤存在困难，而这些金属表现出多种可达到的氧化态。然而，我们最近证明，低价钴催化剂也可用于 ACP 和炔烃的分子内 (3+2) 环加成反应，7c该反应最初是用
• Formation de derives cyclopenteniques et vinylcyclopropaniques lors de la carbopalladation de diesters et d' α-sulfonylesters alleniques
  作者：Mohammed Ahmar、Bernard Cazes、Jacques Gore

  DOI：10.1016/s0040-4020(01)81636-7

  日期：1987.1
• Synthesis of Enantioenriched Allenes from 1,1-Cyclopropanediesters
  作者：Pascal Cérat、Philipp J. Gritsch、Sébastien R. Goudreau、André B. Charette

  DOI：10.1021/ol902766f

  日期：2010.2.5

  Highly substituted allenes were obtained by the S(N)2' addition of organocuprate reagents on 2-propargyl-1,1-cyclopropanediesters. This new methodology permits the synthesis of highly enantioenriched allenes as the reaction proceeds with retention of the enantiomeric purity of the starting cyclopropane. The use of higher order cuprates was instrumental in obtaining the reported results.
• Access to the Protoilludane Core by Gold-Catalyzed Allene-vinylcyclopropane Cycloisomerization
  作者：Anthony Pitaval、David Leboeuf、Julien Ceccon、Antonio M. Echavarren

  DOI：10.1021/ol402188b

  日期：2013.9.6

  Gold(I)-catalyzed allene-vinylcyclopropane cycloisomerization leads to the tricyclic framework of the protoilludanes in a single step by a reaction that involves a cyclopropane ring expansion and a Prins cyclization.