2,2-bis-(4-methyl-pent-2-ynyl)-malonic acid dimethyl ester | 489448-35-3

• 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: 2,2-bis-(4-methyl-pent-2-ynyl)-malonic acid dimethyl ester
• 英文别名: 6,6-di(methoxycarbonyl)-2,10-dimethyl-3,8-undecadiyne；dimethyl 2,2-bis(4-methylpent-2-yn-1-yl)malonate；Dimethyl bis(4-methylpent-2-yn-1-yl)propanedioate；dimethyl 2,2-bis(4-methylpent-2-ynyl)propanedioate
• CAS: 489448-35-3
• 化学式: C₁₇H₂₄O₄
• 分子量: 292.375
• InChiKey: AMKGVKBEOBKNRA-UHFFFAOYSA-N

物化性质

• 沸点：
  377.2±42.0 °C(Predicted)
• 密度：
  1.031±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.65
• 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：

  2,2-bis-(4-methyl-pent-2-ynyl)-malonic acid dimethyl ester 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer silver tetrafluoroborate 、 偶氮二异丁腈 、 三(三甲基硅基)硅烷 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 1,2-二氯乙烷 、 苯 为溶剂， 反应 24.0h， 生成 [2,2-di(methoxycarbonyl)-6-(2-methoxy-1-naphthyl)-4,7-di(1-methylethyl)-5-indanyl]diphenylphosphine
  参考文献：
  名称：

  通过铑催化的缩合二炔与 1-炔基膦硫化物的 [2 + 2 + 2] 环加成反应合成大块膦

  摘要：

  系链二炔与 1-炔基硫化膦在铑催化下的反应提供了相应的具有庞大芳基的硫化膦。下面的脱硫作用产生大的膦，它们可能在过渡金属催化的反应中用作配体。

  DOI：

  10.1021/ja071622o

文献信息

• Rhodium-Catalyzed Arylative Cyclization Reaction of Diynes with Arylboronic Acids
  作者：Masahiro Murakami、Tomoya Miura、Motoshi Yamauchi

  DOI：10.1055/s-2007-984879

  日期：——

  Diynes having malonate-based tethers react with aryl­boronic acids in the presence of a rhodium(I) catalyst to give 1,2-dialkylidenecycloalkanes. The regioselectivity of the initial carbo­rhodation depends on the sterics and the directing nature of the alkyne substituents.

  在铑(I)催化剂的作用下，具有丙二酸系的二炔与芳基硼酸发生反应，生成 1,2-二烷基亚烷基环烷。初始羰基化反应的区域选择性取决于炔取代基的立体性和定向性。
• Nickel-Catalyzed Cycloaddition of Alkynes and Isocyanates
  作者：Hung A. Duong、Michael J. Cross、Janis Louie

  DOI：10.1021/ja046477i

  日期：2004.9.1

  A mild and general route for preparing 2-pyridones from isocyanates and diynes is described. Ni imidazolyidene complexes were used to mediate cyclizations between both internal and terminal diynes with aryl and alkyl isocyanates. In addition, the efficacy of this protocol allows for the preparation of a fused seven-membered pyridone and for three component cyclizations.
• Efficient Nickel-Catalyzed [2 + 2 + 2] Cycloaddition of CO₂ and Diynes
  作者：Janis Louie、John E. Gibby、Marc V. Farnworth、Thomas N. Tekavec

  DOI：10.1021/ja027438e

  日期：2002.12.1

  A mild and general route for preparing 2-pyrones from CO2 and diynes is described. Under only 1 atm of CO2, excellent yields of pyrone are obtained using catalytic amounts of Ni(COD)2 and imidazolylidene ligand, IPr. In addition, stoichiometric reactions between the isolated complex Ni(IPr)2, diynes, and CO2 suggest that the pathway involves initial reaction with CO2 as the key step.
• Rhodium-Catalyzed Decarboxylative Cycloaddition Route to Substituted Anilines
  作者：Kainan Zhang、Janis Louie

  DOI：10.1021/jo200236h

  日期：2011.6.3

  A convenient method for preparing substituted anilines via a Rh-catalyzed [2 + 2 + 2] cycloaddition reaction of diynes and 2-oxazolone was discovered. The initial cycloaddition adducts undergo facile decarboxylation of carbon dioxide to afford aniline products. Reaction conditions are mild, and only 3 mol % Rh catalyst is required. High regioselectivity was observed when an unsymmetrical diyne was used as a starting material.