methyl cyano-β-acrylate

• 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: methyl cyano-β-acrylate
• 英文别名: Methyl 3-cyano-acrylate；methyl 3-cyanoprop-2-enoate
• 化学式: C₅H₅NO₂
• 分子量: 111.1
• InChiKey: AJXIQWIGXITQSV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  对甲基苯磺酰甲基异腈 、 methyl cyano-β-acrylate 在 sodium t-butanolate 作用下， 以 二甲基亚砜 为溶剂， 生成 methyl 4-cyanopyrrole-3-carboxylate
  参考文献：
  名称：

  Controllable Skeletal and Peripheral Editing of Pyrroles with Vinylcarbenes

  摘要：

  The skeletal editing of azaarenes through insertion, deletion, or swapping of single atoms has recently gained considerable momentum in chemical synthesis. Here, we describe a practical skeletal editing strategy using vinylcarbenes in‐situ generated from trifluoromethyl vinyl N‐triftosylhydrazones, leading to the first dearomative skeletal editing of pyrroles through carbon‐atom insertion. Furthermore, depending on the used catalyst and substrate, three types of peripheral editing reactions of pyrroles are also disclosed: α‐ or γ‐selective C–H insertion, and [3+2] cycloaddition. These controllable molecular editing reactions provide a powerful platform for accessing medicinally relevant CF3‐containing N‐heterocyclic frameworks, such as 2,5‐dihydropyridines, piperidines, azabicyclo[3.3.0]octadienes, and allylated pyrroles from readily available pyrroles. Mechanistic insights from experiments and density functional theory (DFT) calculations shed light on the origin of substrate‐ or catalyst‐controlled chemo‐ and regioselectivity as well as the reaction mechanism.

  DOI：

  10.1002/anie.202401359
• 作为产物：
  描述：

  甲醇 、 氰化钠 、 2-丙炔-1-醇 在 manganese(IV) oxide 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以19%的产率得到methyl cyano-β-acrylate
  参考文献：
  名称：

  使用二氧化锰 (IV) 的活性醇中的酯和酰胺：串联氧化工艺

  摘要：

  二氧化锰 (IV) 可与氰化钠一起在 THF-甲醇中或单独在甲醇中用于将活化的醇直接转化为甲酯。也可以制备乙酯和异丙酯。类似地，在含有氨或伯胺的 THF 中使用二氧化锰 (IV) 和氰化钠可用于将醇转化为相应的酰胺。报道了几种活化醇和一种非活化醇的例子。

  DOI：

  10.1055/s-2003-39163

文献信息

• Cyanovinylation of Aldehydes: Organocatalytic Multicomponent Synthesis of Conjugated Cyanomethyl Vinyl Ethers
  作者：Samuel Delgado-Hernández、Fernando García-Tellado、David Tejedor

  DOI：10.3390/molecules26144120

  日期：——

  A novel organocatalytic multicomponent cyanovinylation of aldehydes was designed for the synthesis of conjugated cyanomethyl vinyl ethers. The reaction was implemented for the synthesis of a 3-substituted 3-(cyanomethoxy)acrylates, using aldehydes as substrates, acetone cyanohydrin as the cyanide anion source, and methyl propiolate as the source of the vinyl component. The multicomponent reaction is

  设计了一种新型的醛的有机催化多组分氰乙烯基化，用于合成共轭氰甲基乙烯基醚。该反应用于合成 3-取代的 3-（氰基甲氧基）丙烯酸酯，使用醛作为底物，丙酮氰醇作为氰化物阴离子源，丙炔酸甲酯作为乙烯基组分的源。多组分反应由N-甲基吗啉 (2.5 mol%)催化，以优异的收率和E-异构体。多组分反应歧管对醛（脂肪族、芳香族、杂芳香族）的结构和组成具有高度耐受性，并且仪器简单（一批，开放气氛）、经济（2.5 mol% 催化剂、化学计量试剂）、环境友好（没有有毒废物），并且可持续（易于扩展）。
• Process for the preparation of organic compounds with imide catalysts
  申请人：Daicel Chemical Industries, Ltd.

  公开号：US07183423B1

  公开（公告）日：2007-02-27

  (A) A compound capable of forming a stable radical and selected from (A1) oxygen-atom-containing compounds each having a carbon-hydrogen bond at the adjacent position to an oxygen atom, (A2) carbonyl-group-containing compounds, and (A3) compounds each having a hydrocarbon group with a methine carbon atom is allowed to react with (B) a radical scavenging compound selected from, for example, (B1) unsaturated compounds, and (B2) compounds each having a hydrocarbon group with a methine carbon atom, in the presence of molecular oxygen by catalysis of, for example, an imide compound shown by the following formula (1): wherein each of R1 and R2 is a hydrogen atom or the like, where R1 and R2 may be combined to form a double bond, or an aromatic or non-aromatic ring; X is an oxygen atom or a hydroxyl group, to yield a product of an addition or substitution reaction of the compound (A) and the compound (B) or its oxidized product. The process can efficiently produce a variety of organic compounds by an addition or substitution reaction using molecular oxygen under mild conditions.

  (A) 从以下化合物中选择一个能够形成稳定自由基的化合物：(A1) 含有氧原子的化合物，其邻近氧原子处有碳氢键，(A2) 含有羰基的化合物，和 (A3) 含有甲烷碳原子的碳氢基团化合物。将其与 (B) 自由基清除化合物反应，该化合物可从以下化合物中选择：(B1) 不饱和化合物，和 (B2) 含有甲烷碳原子的碳氢基团化合物，在分子氧的存在下通过以下式(1)所示的亚酰化合物的催化作用下进行反应：其中R1和R2分别为氢原子或类似物，其中R1和R2可以结合形成双键，或芳香或非芳香环; X为氧原子或羟基，从而生成化合物(A)和化合物(B)或其氧化产物的加成或取代反应产物。该过程可以在温和条件下使用分子氧进行加成或取代反应，高效地产生各种有机化合物。