(4aR*,11S*,11aR*)-5,11a-cis-11,11a-syn-3-(methylthio)-Δ¹⁽²⁾-8,9-(methylenedioxy)-5,11-methanomorphanthridine | 144633-48-7

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: (4aR*,11S*,11aR*)-5,11a-cis-11,11a-syn-3-(methylthio)-Δ¹⁽²⁾-8,9-(methylenedioxy)-5,11-methanomorphanthridine
• 英文别名: (1R,13S,18S)-15-methylsulfanyl-5,7-dioxa-12-azapentacyclo[10.6.1.02,10.04,8.013,18]nonadeca-2,4(8),9,16-tetraene
• CAS: 144633-48-7
• 化学式: C₁₇H₁₉NO₂S
• 分子量: 301.409
• InChiKey: MOVMKEFXBGEPTD-IQVOKHDLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  47
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (1R*,1'S*,2R*,4S*,5R*)-2-<2'-acetoxy-1'-<3'',4''-(methylenedioxy)phenyl>ethyl>-4,5-diacetoxy-1-cyclohexyl-N-tosylamide 在 甲烷磺酸 、 二甲基硫 、 三氟化硼乙醚 、 sodium methylate 、 乙酸酐 、 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 、 红铝 作用下， 以 甲醇 、 二氯甲烷 、 氯仿 、 邻二甲苯 、 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 23.0h， 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

文献信息

• 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
  作者：Miyuki Ishizaki、Osamu Hoshino、Yoichi Iitaka

  DOI：10.1021/jo00052a051

  日期：1992.12

  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.