stemaphylline | 1151666-69-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - Pyrroloazepines
• 英文名称: stemaphylline
• 英文别名: (3R,5S)-3-methyl-5-((R)-2-((9R,9aS)-octahydro-1H-pyrrolo[1,2-a]azepin-9-yl)propyl)dihydrofuran-2(3H)-one；(3R,5S)-5-[(2R)-2-[(9R,9aS)-2,3,5,6,7,8,9,9a-octahydro-1H-pyrrolo[1,2-a]azepin-9-yl]propyl]-3-methyloxolan-2-one
• CAS: 1151666-69-1
• 化学式: C₁₇H₂₉NO₂
• 分子量: 279.423
• InChiKey: MQYIKLXMSSMGLX-LJIZCISZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  stemaphylline 在 sodium tungstate 、 双氧水 作用下， 以 甲醇 为溶剂， 以3 mg的产率得到stemaphylline-N-oxide
  参考文献：
  名称：

  Alkaloids from the Roots of Stemona aphylla

  摘要：

  Three known compounds, stemofoline (1), (2'S)-hydroxystemofoline (2), and (11Z)-1',2'-didehydrostemofoline (3), along with two new alkaloids. stemaphylline (4) and stemaphylline-N-oxide (5), have been isolated from a root extract of Stemona aphylla. The structures of these alkaloids were determined on the basis of their spectroscopic data. The analysis of the crude dichloromethane extract by GC-MS in the EIMS mode showed the presence of alkaloids 1-4, the alkaloid 11, and stilbostemin R (12). The crude dichloromethane extract and 4 were tested for their comparative biological activities. The results of their acetylcholinesterase (AChE) inhibitory activities showed that the crude extract had higher activity than that of 4. The insecticidal properties of the crude extract and 4, using a topical application, showed that 4 had an activity similar to the positive control, methomyl, whereas the crude extract had much lower activity. Their antimicrobial activity against Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 25923, Pseudomonas auruginosa ATCC 27853, and Candida albicans ATCC 90028 was weak (MIC 62.5-125 mu g/mL, MBC 125-250 mu g/mL, MFC 125 mu g/mL) but much higher than that of the crude extract.

  DOI：

  10.1021/np900030y
• 作为产物：
  描述：

  (R)-4-(tert-butyldiphenylsilyloxy)-2-methylbutan-1-ol 在 盐酸 、 platinum(IV) oxide 、 tris(triphenylphosphine)ruthenium(II) chloride 、 正丁基锂 、 偶氮二甲酸二异丙酯 、 混旋樟脑磺酸 、 四丁基氟化铵 、 氢气 、 仲丁基锂 、 potassium carbonate 、 三苯基膦 、 三氟乙酸 、 potassium iodide 、 (+)-鹰爪豆碱 、 (+)-sparteine surrogate 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 191.16h， 生成 stemaphylline
  参考文献：
  名称：

  (−)-Stemaphylline 的立体控制全合成

  摘要：

  即使使用良好的离去基团 (Cl - )，容易获得的 α-硼基吡咯烷与金属类胡萝卜素的同系化也特别具有挑战性。通过进行从 Et 2 O 到 CHCl 3 的溶剂转换，中间体硼酸酯与卤化物和酯离去基团发生有效的 1,2-金属盐重排。该方法用于百部生物碱 (−)-Stemaphylline 的全合成，仅需 11 个步骤（最长的线性序列），具有高立体控制（>20:1 dr）和 11% 的总产率。该合成还具有与含类胡萝卜素的叔胺进行后期锂化-硼化反应的特点。

  DOI：

  10.1002/anie.201611273

文献信息

• Total Synthesis of Stemaphylline<i>N</i>-Oxide and Related C9a-Epimeric Analogues
  作者：Michael L. Schulte、Mark L. Turlington、Sharangdhar S. Phatak、Joel M. Harp、Shaun R. Stauffer、Craig W. Lindsley

  DOI：10.1002/chem.201302669

  日期：2013.9.2

  Winning the relay: The first total synthesis of stemaphylline N-oxide has been completed utilizing a bistandem relay ring-closing-metathesis (RRCM) strategy, necessitated by the conformation of the requisite tetraene. This effort also gave unnatural 9a-epi-stemaphylline and 9a-epi-stemaphylline N-oxide.
• Stereocontrolled Total Synthesis of (−)-Stemaphylline
  作者：Ana Varela、Lennart K. B. Garve、Daniele Leonori、Varinder K. Aggarwal

  DOI：10.1002/anie.201611273

  日期：2017.2.13

  to CHCl3, efficient 1,2‐metalate rearrangement of the intermediate boronate occurs with both halide and ester leaving groups. The methodology was used in the total synthesis of the Stemona alkaloid (−)‐stemaphylline in just 11 steps (longest linear sequence), with high stereocontrol (>20:1 d.r.) and 11 % overall yield. The synthesis also features a late‐stage lithiation–borylation reaction with a tertiary

  即使使用良好的离去基团 (Cl - )，容易获得的 α-硼基吡咯烷与金属类胡萝卜素的同系化也特别具有挑战性。通过进行从 Et 2 O 到 CHCl 3 的溶剂转换，中间体硼酸酯与卤化物和酯离去基团发生有效的 1,2-金属盐重排。该方法用于百部生物碱 (−)-Stemaphylline 的全合成，仅需 11 个步骤（最长的线性序列），具有高立体控制（>20:1 dr）和 11% 的总产率。该合成还具有与含类胡萝卜素的叔胺进行后期锂化-硼化反应的特点。
• Alkaloids from the Roots of <i>Stemona aphylla</i>
  作者：Pitchaya Mungkornasawakul、Sukanda Chaiyong、Thanapat Sastraruji、Araya Jatisatienr、Chaiwat Jatisatienr、Stephen G. Pyne、Alison T. Ung、John Korth、Wilford Lie

  DOI：10.1021/np900030y

  日期：2009.5.22

  Three known compounds, stemofoline (1), (2'S)-hydroxystemofoline (2), and (11Z)-1',2'-didehydrostemofoline (3), along with two new alkaloids. stemaphylline (4) and stemaphylline-N-oxide (5), have been isolated from a root extract of Stemona aphylla. The structures of these alkaloids were determined on the basis of their spectroscopic data. The analysis of the crude dichloromethane extract by GC-MS in the EIMS mode showed the presence of alkaloids 1-4, the alkaloid 11, and stilbostemin R (12). The crude dichloromethane extract and 4 were tested for their comparative biological activities. The results of their acetylcholinesterase (AChE) inhibitory activities showed that the crude extract had higher activity than that of 4. The insecticidal properties of the crude extract and 4, using a topical application, showed that 4 had an activity similar to the positive control, methomyl, whereas the crude extract had much lower activity. Their antimicrobial activity against Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 25923, Pseudomonas auruginosa ATCC 27853, and Candida albicans ATCC 90028 was weak (MIC 62.5-125 mu g/mL, MBC 125-250 mu g/mL, MFC 125 mu g/mL) but much higher than that of the crude extract.