(1S*,4S*,8S*,11R*)-3,11-dimethyl-3-azatricyclo<6.2.1.04,11>undec-5-en-2-one | 118574-41-7

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (1S*,4S*,8S*,11R*)-3,11-dimethyl-3-azatricyclo<6.2.1.04,11>undec-5-en-2-one
• 英文别名: (1S^*,4S^*,8S^*,11R^*)-3,11-dimethyl-3-azatricyclo<6.2.1.0^4,11>undec-5-en-2-one
• CAS: 118574-41-7
• 化学式: C₁₂H₁₇NO
• 分子量: 191.273
• InChiKey: YBFLDJBSOVLOAH-GUDRVLHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.82
• 重原子数：
  14.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  20.31
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  2-methyl-2-cyclopentene-1-carboxylic acid chloride 在 N,N-二乙基苯胺 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 (1S*,4S*,8S*,11R*)-3,11-dimethyl-3-azatricyclo<6.2.1.04,11>undec-5-en-2-one
  参考文献：
  名称：

  General methods for alkaloid synthesis via intramolecular Diels-Alder reactions. A concise formal total synthesis of (.+-.)-dendrobine

  摘要：

  DOI：

  10.1021/jo00263a002

文献信息

• Applications of intramolecular Diels-Alder reactions to alkaloid synthesis. A formal total synthesis of (.+-.)-dendrobine
  作者：Stephen F. Martin、Wei Li

  DOI：10.1021/jo00002a029

  日期：1991.1

  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.