dimethyl (2-methyl-2-propenyl)-propanedioate | 50598-40-8

• 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: dimethyl (2-methyl-2-propenyl)-propanedioate
• 英文别名: dimethyl 2-(2-methylallyl)malonate；dimethyl (methallyl)malonate；Propanedioic acid, (2-methyl-2-propenyl)-, dimethyl ester；dimethyl 2-(2-methylprop-2-enyl)propanedioate
• CAS: 50598-40-8
• 化学式: C₉H₁₄O₄
• 分子量: 186.208
• InChiKey: JTNDZINZKNRYIT-UHFFFAOYSA-N

物化性质

• 沸点：
  187.4±20.0 °C(Predicted)
• 密度：
  1.038±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2917190090

反应信息

• 作为反应物：
  描述：

  dimethyl (2-methyl-2-propenyl)-propanedioate 在 甲醇 、 potassium hydroxide 、 二甲基亚砜 作用下， 反应 24.0h， 以94%的产率得到4-甲基-4-戊酸
  参考文献：
  名称：

  Synthesis of Small and Large Fused Bicyclic Compounds by Tandem Dienyne Ring-Closing Metathesis

  摘要：

  A tandem ring-closing metathesis reaction using ruthenium catalyst was carried out to synthesize various fused bicyclic compounds containing both small and large rings. Fast ring-closure of the small ring and slow ring-closure of the large ring resulted in the formation of only one Isomer. Further manipulation such as the Diels-Alder reaction was carried out to prepare a complex molecule containing multiple rings of different sizes.

  DOI：

  10.1021/ol101233k
• 作为产物：
  描述：

  炔丙基丙二酸二甲酯 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 氢碘酸 作用下， 以 乙醚 、 水 为溶剂， 反应 16.0h， 生成 dimethyl (2-methyl-2-propenyl)-propanedioate
  参考文献：
  名称：

  Iridium-catalyzed hydroiodination of functionalized alkynes

  摘要：

  The efficiency of an Ir(I)/HI system has been studied. The association of hydroiodic acid with iridium has been tested in the catalytic hydroiodination of alkynes. The use of [Ir(cod)Cl](2) dimer led to clean hydroiodination reactions and afforded the corresponding vinyliodides as a mixture of derivatives, where the Markovnikov type adduct was found to be the major product (80/20 to 93/7 ratio), in good yields. The mechanism was investigated and two main pathways seemed to be involved, one based on an initial oxidative addition of HI to the Ir(I) complex and the other one based on a pi-activation of the alkyne moiety. The corresponding vinyliodides were engaged in Pd-catalyzed cross-coupling (Sonogashira and Suzuki-Miyaura) reactions under organoaqueuous conditions. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2010.10.052

文献信息

• Palladium catalysed tandem cyclisation-anion capture processes. Part 1. Background and hydride ion capture by alkyl- and π-allyl-palladium species.
  作者：Barry Burns、Ronald Grigg、Vijayaratnam Santhakumar、Visuvanathar Sridharan、Paul Stevenson、Tanachet Worakun

  DOI：10.1016/s0040-4020(01)88268-5

  日期：1992.1

  A new, wide ranging, synthetically powerful, catalytic tandem cyclisation-anion capture process is proposed which depends on the rate of cyclisation of an organopalladium specifies (RPdX) onto a proximate alkene or diene being significantly faster than anion exchange and reductive elimination in the sequence RPdX → RPdY → RY + Pd(0). The catalytic cyclisation - anion capture sequence is illustrated

  提出了一种新的，范围广泛，合成功能强大的催化串联环化-阴离子捕获方法，该方法取决于有机钯化合物（RPdX）在近邻烯烃或二烯上环化的速率明显快于顺序中的阴离子交换和还原消除RPdX→RPdY→RY + Pd（0）。举例说明了催化环化-阴离子捕获序列可通过多种底物捕获氢化物，从而产生稠合和螺环，碳和杂环系统，以及区域和立体特异性。
• Nickel/Zinc Chloride-Promoted Domino Reaction of Enynes and Enones Including Unstrained CC Bond Cleavage
  作者：Kaori Ambe-Suzuki、Yukari Ohyama、Naohiro Shirai、Shin-ichi Ikeda

  DOI：10.1002/adsc.201100770

  日期：2012.3.16

  Unstrained CC bond cleavage proceeds during the domino reaction of enynes and enones that includes successive CC bond formation under the nickel/zinc/zinc chloride system. The cleavage occurs through β‐syn‐elimination of the 1,3‐dicarbonyl part. In addition, β‐carbon elimination is selective, unlike the β‐hydrogen elimination in the presence of excess zinc chloride.

  非应变Ç 烯炔和烯酮的多米诺反应，其包括连续℃持续C键的裂解前进镍/锌/氯化锌系统下C键的形成。裂解是通过1，3-二羰基部分的β同步消除而发生的。另外，β-碳的消除是选择性的，这与在过量氯化锌存在下的β-氢的消除不同。
• [EN] 6-HETEROARYLOXY BENZIMIDAZOLES AND AZABENZIMIDAZOLES AS JAK2 INHIBITORS<br/>[FR] 6-HÉTÉROARYLOXY BENZIMIDAZOLES ET AZABENZIMIDAZOLES EN TANT QU'INHIBITEURS DE JAK2
  申请人：AJAX THERAPEUTICS INC

  公开号：WO2021226261A1

  公开（公告）日：2021-11-11

  The present disclosure provides 6-heteroaryloxy benzimidazole and azabenzimidazole compounds and compositions thereof useful for inhibiting JAK2.

  本公开提供了6-杂芳氧基苯并咪唑和氮杂苯并咪唑化合物及其组合物，用于抑制JAK2。
• Chiral Hetero- and Carbocyclic Compounds from the Asymmetric Hydrogenation of Cyclic Alkenes
  作者：J. Johan Verendel、Jia-Qi Li、Xu Quan、Byron Peters、Taigang Zhou、Odd R. Gautun、Thavendran Govender、Pher G. Andersson

  DOI：10.1002/chem.201104073

  日期：2012.5.21

  Several types of chiral hetero‐ and carbocyclic compounds have been synthesized by using the asymmetric hydrogenation of cyclic alkenes. N,P‐Ligated iridium catalysts reduced six‐membered cyclic alkenes with various substituents and heterofunctionality in good to excellent enantioselectivity, whereas the reduction of five‐membered cyclic alkenes was generally less selective, giving modest enantiomeric

  通过使用环状烯烃的不对称氢化，已经合成了几种类型的手性杂环和碳环化合物。N，P连接的铱催化剂将具有各种取代基和杂官能团的六元环烯烃还原为良好至优异的对映选择性，而五元环烯烃的还原通常选择性较低，给出适度的对映异构体过量。氢化的立体选择性在很大程度上取决于五元环烯烃而不是六元环烯烃的底物结构。六元烯烃还原反应中形成的主要对映异构体可通过选择性模型预测，异构体烯烃具有互补的对映选择性，氢化后可得到相反的旋光异构体。顺式环己烷羧酸盐。
• Rhodium Complex-Catalyzed Cycloisomerization of Allenenes:  Exo and Endo Cyclization Depending on the Auxiliary Ligands
  作者：Tatsuya Makino、Kenji Itoh

  DOI：10.1021/jo035551x

  日期：2004.1.1

  having an exo-alkylidene moiety. In this cycloisomerization, (E)- and (Z)-allenenes are transformed stereospecifically to the corresponding cyclic (E)- and (Z)-1,4-dienes, respectively. On the other hand, the reactions under carbon monoxide atmosphere exclusively afford seven-membered-ring products through an endo-mode cyclization. The unusual cyclization involves an allylic C−H activation process. The

  在催化量的铑（I）配合物的存在下，丙二烯进行环异构化反应，导致选择性地形成外亚烷基亚碳环和杂环。在铑配合物的三芳基亚磷酸酯，环状1,4-或1,5-二烯的催化体系是通过具有所述金属环中间形成良好至优异的产量在正规外-环化模式外-亚烷基部分。在这种环异构化中，（E）-和（Z）-烯丙烯立体定向转化为相应的环状（E）-和（Z）-1,4-二烯分别。另一方面，在一氧化碳气氛下的反应通过内模环化仅提供七元环产物。异常环化涉及烯丙基CH活化过程。在烯基末端带有硅取代基的烯丙基结合一氧化碳，得到相应的[2 + 2 + 1]环加成产物。该结果显然表明铑配合物的催化作用是通过烯丙烯的氧化环化来提供的，以在催化的第一阶段提供关键的外亚烷基亚金属环中间体。