N-ethoxycarbonylpent-4-enylamine | 67902-36-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-ethoxycarbonylpent-4-enylamine
• 英文别名: N-Carbethoxy-4-pentenylamine；ethyl (4-pentenyl)carbamate；ethyl 4-pentenylcarbamate；ethyl N-pent-4-enylcarbamate
• CAS: 67902-36-7
• 化学式: C₈H₁₅NO₂
• 分子量: 157.213
• InChiKey: MXKXZVJYSVEZSA-UHFFFAOYSA-N

物化性质

• 沸点：
  90 °C(Press: 2.3 Torr)
• 密度：
  0.935±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-ethoxycarbonylpent-4-enylamine 在 三氟化硼乙醚 、 一水合肼 、 三氟乙酸 作用下， 以 乙醇 为溶剂， 反应 1.17h， 生成 1-(ethoxycarbonyl)-2-<(phenyltelluro)methyl>pyrrolidine
  参考文献：
  名称：

  Organotelluriums. 20. Aminotellurinylation of olefins and its utilization for synthesis of 2-oxazolidinones

  摘要：

  DOI：

  10.1021/jo00279a031
• 作为产物：
  描述：

  4-Penten-1-胺 、 氯甲酸乙酯 以 四氢呋喃 、 水 为溶剂， 以2.59 g的产率得到N-ethoxycarbonylpent-4-enylamine
  参考文献：
  名称：

  Efficient Regio- and Stereoselective Formation of Azocan-2-ones via 8-Endo Cyclization of α-Carbamoyl Radicals

  摘要：

  The iodine-atom-transfer 8-endo cyclization of alpha-carbamoyl radicals was investigated experimentally and theoretically. With the aid of Mg(ClO4)(2) and a bis(oxazoline) ligand, N-ethoxycarbonyl-substituted N-(pent-4-enyl)-2-iodoalkanamides underwent 8-endo cyclization leading to the formation of only the corresponding 3,5-trans-substituted azocan-2-ones in excellent yields Similarly, the BF3 center dot OEt2/H2O-promoted reactions of N-ethoxycarbonyl-N-(2-allylaryl)-2-iodoalkanamides afforded exclusively the benzazocanone products with a 3,5-cis configuration in high yields The bidentate chelation of substrate radicals not only significantly improved the efficiency of cyclization but also resulted in the change of stereochemistry of azocanone products from 3,8-trans to 3,8-cis Theoretical calculations at the UB3LYP/6-31G* level revealed that the cyclization of N-carbonyl-substituted alpha-carbamoyl radicals occurs via the E-conformational transition states without the presence of a Lewis acid. On the other hand, the cyclization proceeds via the Z-conformational transition states when the substrates form the bidentate chelation with a Lewis acid In both cases, the 8-endocyclization is always fundamentally preferred over the corresponding 7-exo cyclization The complexed radicals having the more rigid conformations also allow the better stereochemical control in the iodine-atom-abstraction step To further understand the reactivity of alpha-carbamoyl radicals, the competition between the 8-endo and 5-exo cyclization was also studied The results demonstrated that the 8-endo cyclization is of comparable rate to the corresponding 5-exo cyclization for alpha-carbamoyl radicals with fixed Z-conformational transition states As a comparison, the 8-endo mode is fundamentally preferred over the 5-exo mode in the cyclization of INIH-amide substrates because the latter requires the Z-conformational transition states, whereas the former proceeds via the more stable E-conformational transition states.

  DOI：

  10.1021/ja9082649

文献信息

• [EN] PRODRUGS OF MYELOPEROXIDASE INHIBITORS<br/>[FR] PROMÉDICAMENTS D'INHIBITEURS DE LA MYÉLOPEROXYDASE
  申请人：BIOHAVEN THERAPEUTICS LTD

  公开号：WO2021072140A1

  公开（公告）日：2021-04-15

  Disclosed are prodrugs of myeloperoxidase (MPO) inhibitors, methods of treating MPO related disorders, e.g., multiple system atrophy, amyotrophic lateral sclerosis, and Huntingtons disease, and methods of neuroprotection, which include administering to a patient in need thereof the prodrugs, pharmaceutical compositions including the prodrugs, and kits including the pharmaceutical compositions and instructions for use.

  揭示了髓过氧化物酶（MPO）抑制剂的前药，治疗MPO相关疾病的方法，例如多系统萎缩症、肌萎缩侧索硬化和亨廷顿病，以及神经保护方法，包括向需要的患者施用前药，包括前药的药物组合物，以及包括药物组合物和使用说明的工具包。
• The use of chiral diferrocenyl diselenides for highly selective asymmetric intramolecular selenocyclisation
  作者：Hiroya Takada、Yoshiaki Nishibayashi、Sakae Uemura

  DOI：10.1039/a901087d

  日期：——

  Asymmetric intramolecular selenocyclisation of alkenoic acids, alkenols and alkenyl urethanes using chiral 2-[1-(dimethylamino)ethyl]ferrocenylselenenyl cations proceeds smoothly to give the corresponding organoselenenyl moiety-containing lactones, cyclic ethers and N-heterocycles, respectively, in good to excellent chemical yields (up to 97%) with very high diastereoselectivities (up to 98% de). The nature of the counter anions of the selenenylating agents affected remarkably the diastereoselectivity of the cyclisation, PF6– and BF4– being revealed to be the best for alkenoic acids and alkenols, and alkenyl urethanes, respectively. A plausible reaction scheme for the cyclisation is presented where a chiral selenenylating agent approaches the carbon–carbon double bond of the substrate from the less sterically-congested direction to afford a chiral episelenonium ion followed by an intramolecular back side attack of a nucleophile.

  不对称的分子内硒环化反应针对烯酸、烯醇和烯基氨基甲酸酯，采用手性2-[1-(二甲基氨基)乙基]铁烯基硒正离子顺利进行，生成相应的含有有机硒基团的内酯、环醚和氮杂环，化学收率良好到优异（高达97%），且具有非常高的diastereoselectivity（高达98%去对映体选择性）。硒化试剂的反离子性质显著影响了环化反应的diastereoselectivity，PF6–和BF4–分别被证明是烯酸和烯醇、烯基氨基甲酸酯的最佳选择。提出了一个合理的反应机制，其中手性硒化试剂从立体空间上不拥挤的方向靠近底物的碳-碳双键，形成手性的episelenonium离子，随后发生亲核试剂的分子内背面攻击。
• Synthesis and Substitution Reactions of N-Protected 2-(Phenylselenonylmethyl)pyrrolidines
  作者：Matthew A. Cooper、A . David Ward

  DOI：10.1071/c96148

  日期：——

  Alkyl phenyl selenides derived from the benzeneselenenyl chloride induced cyclization of N-protected pent-4-enylamines can be converted in good yield into the corresponding 2-hydroxymethyl- or 2- alkoxymethyl-substituted pyrrolidines by oxidation to the corresponding selenone, followed by reaction with water (or hydroxide) or with the corresponding alcohol. Details of the reactions and possible mechanisms for the substitution are discussed.

  由苯硒酰氯诱导环化生成的烷基苯基硒化物 N-保护的戊-4-烯胺的环化反应，能以良好的收率转化为相应的 2-羟甲基或 2-羟甲基-2-烯胺。 以良好的收率转化为相应的 2-羟甲基或 2-烷氧基甲基取代的吡咯烷酮。 烷氧基甲基取代的吡咯烷，氧化成相应的 硒酮，然后与水（或氢氧化物）或相应的醇反应。 相应的醇进行反应。讨论了反应的细节和可能的 讨论。
• Aminotellurinylation of Olefins with Benzenetellurinyl Acetate and Ethyl Carbamate
  作者：Nan Xing Hu、Yoshio Aso、Tetsuo Otsubo、Fumio Ogura

  DOI：10.1246/cl.1987.1327

  日期：1987.7.5

  Benzenetellurinyl acetate or trifluoroacetate in combination with ethyl carbamate effected aminotellurinylation of olefins in chloroform under reflux in the presence of boron trifluoride etherate to give ethyl [(2-phenyltelluro)alkyl]carbamates in high yields after reduction with hydrazine hydrate. This reaction was extended to cyclofunctionalization of olefinic carbamates into nitrogen heterocycles.

  乙酸苯碲酯或三氟乙酸酯与氨基甲酸乙酯组合，在三氟化硼乙醚存在下，在回流下，在氯仿中进行烯烃的氨基碲酰化，在用水合肼还原后，以高收率得到[(2-苯基碲)烷基]氨基甲酸乙酯。该反应扩展到烯属氨基甲酸酯环官能化成氮杂环。
• Cyclofunctionalization of olefinic urethanes using benzeneselenenyl chloride in the presence of silica gel: a general route to nitrogen heterocycles
  作者：D. L. J. Clive、Vittorio Farina、Alok Singh、Chi Kwong Wong、William A. Kiel、Steven M. Menchen

  DOI：10.1021/jo01299a019

  日期：1980.5