(2S*,3R*,4aR*,11S*,11aR*)-5,11a-cis-11,11a-syn-3-(benzyloxy)-2-hydroxy-8,9-(methylenedioxy)-5,11-methanomorphanthridine | 139039-77-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢异喹啉
• 英文名称: (2S*,3R*,4aR*,11S*,11aR*)-5,11a-cis-11,11a-syn-3-(benzyloxy)-2-hydroxy-8,9-(methylenedioxy)-5,11-methanomorphanthridine
• CAS: 139039-77-3
• 化学式: C₂₃H₂₅NO₄
• 分子量: 379.456
• InChiKey: GLJJFJNFPRZUFI-SSSFQFABSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.05
• 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：
  0.48
• 拓扑面积：
  51.16
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (2S*,3R*,4aR*,11S*,11aR*)-5,11a-cis-11,11a-syn-3-(benzyloxy)-2-hydroxy-8,9-(methylenedioxy)-5,11-methanomorphanthridine 在 二甲基硫 、 三氟化硼乙醚 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 二氯甲烷 、 邻二甲苯 为溶剂， 反应 7.67h， 生成 (4aR*,11S*,11aR*)-5,11a-cis-11,11a-syn-3-(methylthio)-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
• 作为产物：
  描述：

  (1R*,2R*,4S*,5R*)-4,5-diacetoxy-2-<1'-<3'',4''-(methylenedioxy)phenyl>vinyl>-1-cyclohexyl-N-tosylamide 在 吡啶 、 sodium hydroxide 、 硼烷四氢呋喃络合物 、 甲烷磺酸 、 双氧水 、 sodium methylate 、 乙酸酐 、 二异丁基氢化铝 、 对甲苯磺酸 、 红铝 作用下， 以 甲醇 、 氯仿 、 邻二甲苯 、 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 11.91h， 生成 (2S*,3R*,4aR*,11S*,11aR*)-5,11a-cis-11,11a-syn-3-(benzyloxy)-2-hydroxy-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

文献信息

• A first total synthesis of montanine-type amaryllidaceae alkaloids, (±)-coccinine, (±)-montanine, and (±)-pancracine
  作者：Miyuki Ishizaki、Osamu Hoshino、Yoichi Iitaka

  DOI：10.1016/0040-4039(91)85045-7

  日期：1991.11

  Montanine-type Amaryllidaceae alkaloids, (±)-coccinine (1), (±)-montanine (2), and (±)-pancracine (3) were synthesized starting from (±)-1,2-cis-2-(3,4-methylenedioxybenzoyl)cyclohex-4-enecarboxylic acid (6) via (±)-2,3-cis-3-benzyloxy-2-hyroxy-4a,11a-cis-11,11a-syn-5,11-methano-8,9-methylenedioxymorphanthridine (7) as a key compound.

  Montanine型石蒜科生物碱，（±）-coccinine（1），（±）-montanine（2），和（±）-pancracine（3）的合成由（±）-1,2-开始顺式-2-（通过（±）-2,3-顺式-3-苄氧基-2-羟基-4a，11a-顺式-11,11a-syn-5,11-经由（±）-2,3-的3,4-亚甲基二氧苯甲酰基）环己-4-烯羧酸（6）甲醇-8,9-亚甲基二氧基吗啡啶（7）为关键化合物。