(1S^*,4S^*,5R^*,6S^*,8S^*,11R^*)-5,6-epoxy-11-methyl-3-azatricyclo<6.2.1.0^4,11>-2-undecanone | 129872-24-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (1S^*,4S^*,5R^*,6S^*,8S^*,11R^*)-5,6-epoxy-11-methyl-3-azatricyclo<6.2.1.0^4,11>-2-undecanone
• 英文别名: (1S,4S,7S,8R,10S,12R)-12-methyl-9-oxa-6-azatetracyclo[5.4.1.04,12.08,10]dodecan-5-one
• CAS: 129872-24-8
• 化学式: C₁₁H₁₅NO₂
• 分子量: 193.246
• InChiKey: BZZFMXWRGXWPSQ-KTRJATQDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  41.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S^*,4S^*,5R^*,6S^*,8S^*,11R^*)-5,6-epoxy-11-methyl-3-azatricyclo<6.2.1.0^4,11>-2-undecanone 在 potassium tert-butylate 、 magnesium bromide 作用下， 以 乙二醇二甲醚 、 乙醚 为溶剂， 反应 2.5h， 生成 (1S^*,4S^*,5R^*,6R^*,8S^*,11R^*)-6-bromo-3,11-dimethyl-5-hydroxy-3-azatricyclo<6.2.1.0^4,11>-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：

  N-(diphenylmethyl)-N-1',3'-butadienyl-2-methyl-2-cyclopentene-1-carboxylic amide 在 palladium dihydroxide 氢气 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 溶剂黄146 、 xylene 为溶剂， 反应 32.0h， 生成 (1S^*,4S^*,5R^*,6S^*,8S^*,11R^*)-5,6-epoxy-11-methyl-3-azatricyclo<6.2.1.0^4,11>-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

文献信息

• MARTIN, STEPHEN F.;LI, WEI, J. ORG. CHEM., 56,(1991) N, C. 642-650
  作者：MARTIN, STEPHEN F.、LI, WEI

  DOI：——

  日期：——