(3R*,4aR*,11S*,11aR*)-5,11a-cis-11,11a-syn-3-(benzyloxy)-1-chloro-Δ¹⁽²⁾-8,9-(methylenedioxy)-5,11-methanomorphanthridine | 144609-87-0

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 石蒜科生物碱
• 英文名称: (3R*,4aR*,11S*,11aR*)-5,11a-cis-11,11a-syn-3-(benzyloxy)-1-chloro-Δ¹⁽²⁾-8,9-(methylenedioxy)-5,11-methanomorphanthridine
• CAS: 144609-87-0
• 化学式: C₂₃H₂₂ClNO₃
• 分子量: 395.886
• InChiKey: KMTYSWNMQHKDIC-MVIJMRCYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.42
• 重原子数：
  28.0
• 可旋转键数：
  3.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  30.93
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  (2S*,3R*,4aR*,11S*,11aR*)-8,9-(methylenedioxy)-5,11-methanomorphanthridine-2,3-diol 在 苯基氯化硒 、 二异丁基氢化铝 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 氯仿 、 邻二甲苯 、 甲苯 为溶剂， 反应 9.67h， 生成 (3R*,4aR*,11S*,11aR*)-5,11a-cis-11,11a-syn-3-(benzyloxy)-1-chloro-Δ¹⁽²⁾-8,9-(methylenedioxy)-5,11-methanomorphanthridine
  参考文献：
  名称：

  Total synthesis of montanine-type Amaryllidaceae alkaloids, which possess a 5,11-methanomorphanthridine ring system, through cyclization with sodium bis(2-methoxyethoxy)aluminum hydride (SMEAH): the first stereoselective total syntheses of (.+-.)-montanine, (.+-.)-coccinine, (.+-.)-O-acetylmontanine, (.+-.)-pancracine, and (.+-.)-brunsvigine

  摘要：

  The stereoselective total syntheses of the title alkaloids 1-5 from allylic chloride 31 are described. The key steps in the reaction sequences are as follows: (1) stereoselective hydroboration-oxidation of 12 by means of an intramolecular charge-transfer complex to afford alcohol 13 as a single isomer; (2) cyclization of tosylamide alcohol 21 with sodium bis(2-methoxyethoxy)aluminum hydride (SMEAH) to afford functionalized 5,11-methanomorphanthridine 22, which possesses the basic skeleton of montanine-type alkaloids; and (3) conversion of 30a to allylic chloride 31 by treatment with PhSeCl in MeOH under ultrasonication followed by NaIO4 oxidation. A formal total synthesis of (+/-)-manthine (6) was also accomplished.

  DOI：

  10.1021/jo00052a051