ethyl 2-isocyanopent-4-enoate | 166655-28-3

• 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: ethyl 2-isocyanopent-4-enoate
• CAS: 166655-28-3
• 化学式: C₈H₁₁NO₂
• mdl: MFCD11223679
• 分子量: 153.181
• InChiKey: GRYAVDXORXMSEO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  30.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 2-isocyanopent-4-enoate 在 Grubbs catalyst first generation lithium hydroxide 、 sodium hydroxide 、 (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 反应 113.0h， 生成
  参考文献：
  名称：

  Application of tandem Ugi multi-component reaction/ring closing metathesis to the synthesis of a conformationally restricted cyclic pentapeptide

  摘要：

  一种构象受限的环状五肽，含有不饱和的 9 元内酰胺作为半刚性支架，通过串联乌基反应/闭环偏析，以非常趋同的方式制备出来。

  DOI：

  10.1039/b414374d
• 作为产物：
  描述：

  ethyl N-(diphenylmethylene)-2-amino-4-pentenoate 在 盐酸 、 二异丙胺 、 三氯氧磷 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 ethyl 2-isocyanopent-4-enoate
  参考文献：
  名称：

  Thiol Mediated Free Radical Cyclization of Alkenyl and Alkynyl Isocyanides

  摘要：

  Thiol-mediated free radical cyclizations of but-3-enyl and but-3-ynyl isocyanides of types 6-8 give new access to 3,5-disubstituted 2-(alkyl- and 2-(arylthio)pyrrolines 11, 12, and 18. When 2-mercaptoethanol is used with the same isocyanides the reaction results in pyroglutamates 16, 17, or 19. These cyclizations involve the formation of a new carbon-carbon bond through intramolecular addition of a carbon-centered thioimidoyl radical to a carbon-carbon multiple bond. Although cyclic products are usually obtained in high yields, in a few cases a competing radical degradation process leading to isothiocyanates was observed. Isocyanide 8a carrying an allyl(phenyl) sulfide moiety isomerizes to 2-(phenylthio)pyrroline 24 in a series of sequential steps.

  DOI：

  10.1021/jo00104a035

文献信息

• Intramolecular Imidoylative Heck Reaction: Synthesis of Cyclic Ketoimines from Functionalized Isocyanide
  作者：Jian Wang、Shi Tang、Qiang Zhu

  DOI：10.1021/acs.orglett.6b01174

  日期：2016.7.1

  Efficient access to five- to seven-membered cyclic ketoimines, through palladium-catalyzed intramolecular imidoylative Heck reaction of alkene-containing isocyanides, has been developed. Consecutive isocyanide and alkene insertion into aryl or alkyl Pd(II) intermediates takes place in this process. No byproduct derived from monoinsertion or reversed sequence is detected.

  已经开发出通过钯催化含烯烃异氰酸酯的分子内酰亚胺化Heck反应，可以有效地获得五元至七元环状酮亚胺。在此过程中，异氰酸酯和烯烃连续插入芳基或烷基Pd（II）中间体中。没有检测到源自单插入或反向序列的副产物。
• Application of tandem Ugi reaction/ring-closing metathesis in multicomponent synthesis of unsaturated nine-membered lactams
  作者：Luca Banfi、Andrea Basso、Giuseppe Guanti、Renata Riva

  DOI：10.1016/j.tetlet.2003.08.027

  日期：2003.10

  A new straightforward entry into unsaturated nine-membered lactams of potential use as external reverse turn inducers was developed. It is based on an Ugi multicomponent reaction using two unsaturated substrates, followed by highly stereoselective ring-closing metathesis (RCM). The synthesis of a nine-membered secondary lactam by RCM is reported for the first time.

  已经开发出一种新的直接进入不饱和九元内酰胺的方法，该内酰胺可能用作外部反向转导诱导剂。它基于使用两个不饱和底物的Ugi多组分反应，然后进行高度立体选择性的闭环复分解（RCM）。首次报道了通过RCM合成九元仲内酰胺。
• Constrained Phenylalanine Derivatives by Enyne Metathesis and Diels−Alder Reaction
  作者：Sambasivarao Kotha、Nampally Sreenivasachary、Enugurthi Brahmachary

  DOI：10.1002/1099-0690(200102)2001:4<787::aid-ejoc787>3.0.co;2-n

  日期：2001.2

  approach for the synthesis of indane-based α-amino acid derivatives is reported. In this regard, the synthesis of five-membered exocyclic and five-membered inner-outer ring diene building blocks (7 and 15) containing α-amino acid moieties is described. Diene 15 is prepared by an enyne metathesis reaction as a key step. In this paper, a full account of our work regarding the Diels-Alder reaction of these dienes

  报道了一种合成基于茚满的 α-氨基酸衍生物的概念性新方法。在这方面，描述了含有 α-氨基酸部分的五元环外和五元内外环二烯结构单元（7 和 15）的合成。二烯 15 是通过烯炔复分解反应作为关键步骤制备的。在本文中，我们全面介绍了我们关于这些二烯与各种亲二烯体的 Diels-Alder 反应的工作，以及随后环加合物氧化得到各种茚满基 α-氨基酸衍生物的工作。
• Microwave-assisted synthesis of γ-thiolactams from ethyl isocyanoacetate
  作者：Massimiliano Lamberto

  DOI：10.1515/hc-2018-0005

  日期：2018.6.27

  Abstract γ-Thiolactams were synthesized in good yields from ethyl isocyanoacetate through a sequential alkylation/isothiocyanation/radical cyclization under microwave irradiation.

  摘要 以异氰乙酸乙酯为原料，在微波辐照下通过连续烷基化/异硫氰化/自由基环化反应合成了γ-硫内酰胺类化合物，收率良好。
• Synthesis of constrained α-amino acid derivatives via enyne metathesis reaction
  作者：Sambasivarao Kotha、Nampally Sreenivasachary、Enugurthi Brahmachary

  DOI：10.1016/s0040-4039(98)00251-2

  日期：1998.4

  Synthesis of a diene building block via enyne metathesis reaction and its usage in the preparation of constrained alpha-amino acid derivatives is described. (C) 1998 Elsevier Science Ltd. All rights reserved.