(2S*,3R*,4aR*,11S*,11aR*)-2,3-O-isopropylidene-2,3-dihydroxy-8,9-(methylenedioxy)-5-tosylmorphanthridine | 144609-81-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S*,3R*,4aR*,11S*,11aR*)-2,3-O-isopropylidene-2,3-dihydroxy-8,9-(methylenedioxy)-5-tosylmorphanthridine
• CAS: 144609-81-4
• 化学式: C₂₆H₃₁NO₇S
• 分子量: 501.601
• InChiKey: OPHDWJMQLLGXMH-CEFANGEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  35.0
• 可旋转键数：
  3.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  94.53
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (2S*,3R*,4aR*,11S*,11aR*)-2,3-O-isopropylidene-2,3-dihydroxy-8,9-(methylenedioxy)-5-tosylmorphanthridine 在 红铝 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以87.4%的产率得到(2S*,3R*,4aR*,11S*,11aR*)-5,11a-cis-11,11a-syn-2,3-O-isopropylidene-2,3-dihydroxy-8,9-(methylenedioxy)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 、 对甲苯磺酸 作用下， 以 甲醇 、 氯仿 、 1,2-二氯乙烷 为溶剂， 反应 11.0h， 生成 (2S*,3R*,4aR*,11S*,11aR*)-2,3-O-isopropylidene-2,3-dihydroxy-8,9-(methylenedioxy)-5-tosylmorphanthridine
  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