(E)-4-Methyl-1-(1-pyrrolidinyl)-2-pentene | 160890-68-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (E)-4-Methyl-1-(1-pyrrolidinyl)-2-pentene
• 英文别名: 1-((E)-4-methyl-2-pentenyl)pyrrolidine；1-[(E)-4-methylpent-2-enyl]pyrrolidine
• CAS: 160890-68-6
• 化学式: C₁₀H₁₉N
• 分子量: 153.268
• InChiKey: PFNTXVVQUJKXAI-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-4-Methyl-1-(1-pyrrolidinyl)-2-pentene 、 benzyl penta-2,3-dienoate 在 zinc trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 生成 benzyl (2Z,4SR,5RS)-5-isopropyl-4-methyl-3-pyrrolidinohepta-2,6-dienoate 、 benzyl (2E,4SR,5RS)-5-isopropyl-4-methyl-3-pyrrolidinohepta-2,6-dienoate
  参考文献：
  名称：

  一种新的路易斯酸催化的 [3,3]-Sigmatropic 重排的开发：Alenoate-Claisen 重排

  摘要：

  已开发出一种新的路易斯酸催化克莱森重排，它允许从简单的烯丙胺和烯丙酸酯中立体选择性地构建 β-氨基-α、β、ε、zeta-不饱和-γ、δ-二取代酯。该反应取决于使用路易斯酸，可以使用一系列金属盐（Yb(OTf)3、AlCl3、Sn(OTf)2、Cu(OTf)2、MgBr2.Et2O、FeCl3、Zn (OTf)2) 的催化剂负载量低至 5 mol%。这种催化过程可以高产率地获得各种β-氨基-α、β、ε、zeta-不饱和-γ、δ-二取代酯，并且对一系列烯丙基吡咯烷（R1 = H， Me、i-Pr、Ph、NR2 = 吡咯烷、哌啶、NMe2；>/=81% 产率，>/=94:6 顺式：抗）和烯丙酸酯（R2 = H、Me、i-Pr、Ph、烯丙基, NPht, Cl; >/=75% 的产率，>/=91:9 同步：反）。这种新的克莱森重排为难以捉摸的结构基序提供催化途径的能力也已在由香叶基和橙花基吡咯烷

  DOI：

  10.1021/ja028090q
• 作为产物：
  描述：

  4-(1-Methylethyl)-3-<(1-pyrrolidinyl)methyl>-1-oxetan-2-one 生成 (Z)-4-Methyl-1-(1-pyrrolidinyl)-2-pentene 、 (E)-4-Methyl-1-(1-pyrrolidinyl)-2-pentene
  参考文献：
  名称：

  Stereoselective Synthesis of .alpha.-Amino and .alpha.-Thio .beta.-Lactones by Conjugate Addition of Amine and Thiol Nucleophiles to .alpha.-Methylene .beta.-Lactones and Their Decarboxylation to Allylamines and Sulfides

  摘要：

  The stereoselective, conjugate addition of secondary, cyclic amines (pyrrolidine and piperidine) and mercaptans (thiophenol, isopropyl, and benzyl thiols and beta-mercaptoethanol) to alpha-methylene beta-lactones 1 and 2 was investigated. The corresponding alpha-(aminomethyl) and alpha-(thiomethyl) beta-lactones 3-5 and 6-10 were obtained in excellent yields through protonation of the intermediary enolates. In methanol the trans isomers mere the major products, while considerable amounts of the cis isomers were formed in THF and acetone. The decarboxylation of these alpha-aminomethyl and alpha-thiomethyl beta-lactones as neat samples at 180 degrees C produced in excellent yields the corresponding allyl amines and sulfides 11-13 and 14-18 with retention of the initial beta-lactone geometry. This unprecedented sequence of Michael-type addition followed by decarboxylation, in which the alpha-methylene beta-lactones serve as allene equivalents, provides a useful alternative to the Wittig olefination for the preparation of allylic amines and sulfides.

  DOI：

  10.1021/jo00108a019

文献信息

• Linderman, Russell J.; Meyers, A. I., Heterocycles, 1983, vol. 20, # 9, p. 1737 - 1740
  作者：Linderman, Russell J.、Meyers, A. I.

  DOI：——

  日期：——
• Development of a New Lewis Acid-Catalyzed [3,3]-Sigmatropic Rearrangement:  The Allenoate-Claisen Rearrangement
  作者：Tristan H. Lambert、David W. C. MacMillan

  DOI：10.1021/ja028090q

  日期：2002.11.1

  A new Lewis acid-catalyzed Claisen rearrangement has been developed that allows the stereoselective construction of beta-amino-alpha,beta,epsilon,zeta-unsaturated-gamma,delta-disubstituted esters from simple allylic amines and allenoate esters. This reaction, which is contingent upon the use of Lewis acid, can be conducted with a range of metal salts (Yb(OTf)3, AlCl3, Sn(OTf)2, Cu(OTf)2, MgBr2.Et2O

  已开发出一种新的路易斯酸催化克莱森重排，它允许从简单的烯丙胺和烯丙酸酯中立体选择性地构建 β-氨基-α、β、ε、zeta-不饱和-γ、δ-二取代酯。该反应取决于使用路易斯酸，可以使用一系列金属盐（Yb(OTf)3、AlCl3、Sn(OTf)2、Cu(OTf)2、MgBr2.Et2O、FeCl3、Zn (OTf)2) 的催化剂负载量低至 5 mol%。这种催化过程可以高产率地获得各种β-氨基-α、β、ε、zeta-不饱和-γ、δ-二取代酯，并且对一系列烯丙基吡咯烷（R1 = H， Me、i-Pr、Ph、NR2 = 吡咯烷、哌啶、NMe2；>/=81% 产率，>/=94:6 顺式：抗）和烯丙酸酯（R2 = H、Me、i-Pr、Ph、烯丙基, NPht, Cl; >/=75% 的产率，>/=91:9 同步：反）。这种新的克莱森重排为难以捉摸的结构基序提供催化途径的能力也已在由香叶基和橙花基吡咯烷
• Stereoselective Synthesis of .alpha.-Amino and .alpha.-Thio .beta.-Lactones by Conjugate Addition of Amine and Thiol Nucleophiles to .alpha.-Methylene .beta.-Lactones and Their Decarboxylation to Allylamines and Sulfides
  作者：Waldemar Adam、Victor Oswaldo Nava-Salgado

  DOI：10.1021/jo00108a019

  日期：1995.2

  The stereoselective, conjugate addition of secondary, cyclic amines (pyrrolidine and piperidine) and mercaptans (thiophenol, isopropyl, and benzyl thiols and beta-mercaptoethanol) to alpha-methylene beta-lactones 1 and 2 was investigated. The corresponding alpha-(aminomethyl) and alpha-(thiomethyl) beta-lactones 3-5 and 6-10 were obtained in excellent yields through protonation of the intermediary enolates. In methanol the trans isomers mere the major products, while considerable amounts of the cis isomers were formed in THF and acetone. The decarboxylation of these alpha-aminomethyl and alpha-thiomethyl beta-lactones as neat samples at 180 degrees C produced in excellent yields the corresponding allyl amines and sulfides 11-13 and 14-18 with retention of the initial beta-lactone geometry. This unprecedented sequence of Michael-type addition followed by decarboxylation, in which the alpha-methylene beta-lactones serve as allene equivalents, provides a useful alternative to the Wittig olefination for the preparation of allylic amines and sulfides.