N-methyl-N-(4'-methyl-3'-methylene-1'-pentenyl)-2-methyl-2-cyclopentene-1-carboxylic amide | 118495-24-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N-methyl-N-(4'-methyl-3'-methylene-1'-pentenyl)-2-methyl-2-cyclopentene-1-carboxylic amide
• 英文别名: N,2-dimethyl-N-[(E)-4-methyl-3-methylidenepent-1-enyl]cyclopent-2-ene-1-carboxamide
• CAS: 118495-24-2
• 化学式: C₁₅H₂₃NO
• 分子量: 233.354
• InChiKey: AIUMFVNAEZDXQN-MDZDMXLPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.53
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  20.31
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  N-methyl-N-(4'-methyl-3'-methylene-1'-pentenyl)-2-methyl-2-cyclopentene-1-carboxylic amide 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 xylene 为溶剂， 反应 12.0h， 生成 (1S*,4S*,5R*,6S*,8S*,11R*)-3,11-dimethyl-5,6-epoxy-3-azatricyclo<6.2.1.04,11>-2-undecanone
  参考文献：
  名称：

  Applications of intramolecular Diels-Alder reactions to alkaloid synthesis. A formal total synthesis of (.+-.)-dendrobine

  摘要：

  A facile synthesis of the tricyclic enone 3 was completed; since 3 was an intermediate in a previous synthesis of (+/-)-dendrobine (1), this achievement constitutes a formal total synthesis of the racemic title alkaloid. The key strategic element of the approach involved the intramolecular Diels-Alder reaction of the olefinic dienamide 10g, which was prepared by N-acylation of imine 9g with acid chloride 8, to furnish the tricyclic cycloadduct 11g as the major product. Subsequent elaboration of 11g into 3 was then consummated by epoxidation, followed by epoxide rearrangement and oxidation of the intermediate allylic alcohol 23. The synthetic investigations were preceded by a series of model studies that were executed in order to assess the viability and to probe the scope and limitations of the crucial intramolecular [4 + 2] cycloaddition. In these preliminary investigations, we discovered that thermolyses of dienamido olefins 10a-f afforded mixtures (3.5-14:1) of epimeric cycloadducts 11a-f and 12a-f. The steric bulk of the N-alkyl substituent on 10a-d exerted considerable influence upon the energy of activation and the stereochemical course of the respective cycloaddition reactions. A cyclopropyl or isopropyl group positioned at C(8) on the diene moiety of the unsaturated dienamides 10e-g also facilitated the cyclization and enhanced the endo selectivity of the process.

  DOI：

  10.1021/jo00002a029
• 作为产物：
  描述：

  2-甲基环戊-2-烯-1-羧酸 在 草酰氯 、 N,N-二乙基苯胺 作用下， 以 甲苯 、 苯 为溶剂， 反应 2.0h， 生成 N-methyl-N-(4'-methyl-3'-methylene-1'-pentenyl)-2-methyl-2-cyclopentene-1-carboxylic amide
  参考文献：
  名称：

  Applications of intramolecular Diels-Alder reactions to alkaloid synthesis. A formal total synthesis of (.+-.)-dendrobine

  摘要：

  A facile synthesis of the tricyclic enone 3 was completed; since 3 was an intermediate in a previous synthesis of (+/-)-dendrobine (1), this achievement constitutes a formal total synthesis of the racemic title alkaloid. The key strategic element of the approach involved the intramolecular Diels-Alder reaction of the olefinic dienamide 10g, which was prepared by N-acylation of imine 9g with acid chloride 8, to furnish the tricyclic cycloadduct 11g as the major product. Subsequent elaboration of 11g into 3 was then consummated by epoxidation, followed by epoxide rearrangement and oxidation of the intermediate allylic alcohol 23. The synthetic investigations were preceded by a series of model studies that were executed in order to assess the viability and to probe the scope and limitations of the crucial intramolecular [4 + 2] cycloaddition. In these preliminary investigations, we discovered that thermolyses of dienamido olefins 10a-f afforded mixtures (3.5-14:1) of epimeric cycloadducts 11a-f and 12a-f. The steric bulk of the N-alkyl substituent on 10a-d exerted considerable influence upon the energy of activation and the stereochemical course of the respective cycloaddition reactions. A cyclopropyl or isopropyl group positioned at C(8) on the diene moiety of the unsaturated dienamides 10e-g also facilitated the cyclization and enhanced the endo selectivity of the process.

  DOI：

  10.1021/jo00002a029