(6S,10S)-(-)-5,12-dimethyl-9-oxo-6,7,8,9,10,11-hexahydro-6,10-imino-5H-cyclooctindole | 126790-59-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: (6S,10S)-(-)-5,12-dimethyl-9-oxo-6,7,8,9,10,11-hexahydro-6,10-imino-5H-cyclooctindole
• 英文别名: (6S,10S)-5,12-dimethyl-9-oxo-6,7,8,9,10,11-hexahyddfo-6,10-imino-5H-cyclooctindole；(1S,12S)-3,16-dimethyl-3,16-diazatetracyclo[10.3.1.02,10.04,9]hexadeca-2(10),4,6,8-tetraen-13-one
• CAS: 126790-59-8
• 化学式: C₁₆H₁₈N₂O
• 分子量: 254.332
• InChiKey: KSDDMSSIWJFSKR-KBPBESRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  25.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (6S,10S)-(-)-5,12-dimethyl-9-oxo-6,7,8,9,10,11-hexahydro-6,10-imino-5H-cyclooctindole 生成 (6S,10S)-(-)-5,12-dimethyl-9-<<(3-oxo-1-(E)-butenyl)oxy>methyl>-6,7,10,11-tetrahydro-6,10-imino-5H-cyclooctindole
  参考文献：
  名称：

  通过不对称的Pictet-Spengler反应合成大环/ sarpagine相关的吲哚生物碱的一般方法：对映体合成（-）-脱水Macrosalhine-次甲基

  摘要：

  通过不对称的Pictet-Spengler反应，由D-（+）-色氨酸完成了对映体的（-）-脱水甲基甲硫氨酸-次甲基3a的全合成。还已经完成了从天然产物（+）-ajmaline的3a部分合成。

  DOI：

  10.1016/0040-4039(96)01009-x
• 作为产物：
  描述：

  (6S,10S)-(-)-5-methyl-9-oxo-12-benzyl-6,7,8,9,10,11-hexahydro-6,10-imino-5H-cyclooctaindole 在 palladium on activated charcoal 氢气 作用下， 生成 (6S,10S)-(-)-5,12-dimethyl-9-oxo-6,7,8,9,10,11-hexahydro-6,10-imino-5H-cyclooctindole
  参考文献：
  名称：

  合成大分子/ sarpagine生物碱的通用方法。（+）-大麦碱的总合成

  摘要：

  由四环酮5合成了（+）-甲基1和更稳定的当量2。合成中的关键步骤涉及立体选择性Claisen重排，然后对所得烯烃14进行硼氢化氧化，以在C-15和C-16处设置正确的立体化学。

  DOI：

  10.1016/0040-4039(93)88069-u

文献信息

• Enantiospecific Synthesis of (-)-Alstonerine and (+)-Macroline as Well as a Partial Synthesis of (+)-Villalstonine
  作者：Yingzhi Bi、Lin-Hua Zhang、Linda K. Hamaker、James M. Cook

  DOI：10.1021/ja00099a021

  日期：1994.10

  The enantiospecific synthesis of (-)-alstonerine (5) and (+)-macroline (8), as well as a partial synthesis of the Alstonia bisindole alkaloid villalstonine (2) has been completed. In addition, a more stable macroline equivalent 9 was prepared. The stereochemistry at C(15) and C(16) in 5 and 8 has been successfully installed by a stereoselective Claisen rearrangement followed by stereospecific hydroboration-oxidation of the exocyclic methylene function at C-16. The E ring in alstonerine 5 was constructed by a regioselective cyclization followed by a novel Swern oxidation under modified conditions [(COCl)(2)/DMSO/CH2Cl2, -78 degrees C to -10 degrees C/1.5 h; Et(3)N], whereas the C(20)-C(21) enone system in macroline (8) was generated via a convenient one pot process from the beta-diol 45. Condensation of either synthetic (+)-macroline (8) or the macroline equivalent 9 with natural pleiocarpamine 7 in 0.2 N HCl furnished the antiamoebic, antimalarial bisindole alkaloid villalstonine 2. This constitutes the first partial synthesis of any of the Alstonia bisindoles from a synthetically derived indole moiety.
• General approach to the synthesis of macroline-related alkaloids. Stereospecific total synthesis of (-)-alstonerine
  作者：L. H. Zhang、J. M. Cook

  DOI：10.1021/ja00166a084

  日期：1990.5
• ZHANG, L. H.;COOK, J. M., J. AMER. CHEM. SOC., 112,(1990) N0, C. 4088-4090
  作者：ZHANG, L. H.、COOK, J. M.

  DOI：——

  日期：——
• Studies Directed toward the Enantiospecific Synthesis of Gardneria, Voacanga, and Alstonia Oxindole Alkaloids
  作者：Andrew C. Peterson、James M. Cook

  DOI：10.1021/jo00106a024

  日期：1995.1

  A method has been developed to convert N-a-methylmacroline-related indoles into their corresponding oxindoles with a high degree of diastereoselectivity. Prudent choice of the osmium reagent led to the stereoselective conversion of (-)-5-methyl-9-oxo-12-benzyl-6,7,8,9,11-hexahydro-6,10-imino-5H-cyclooct[b]indole (14a) into either diastereomeric N-b-benzyltetracyclic oxindole 21a or 24a. Treatment of racemic or (-)-N-b-benzyl ketone 14a with osmium tetraoxide in the absence of amino ligands led to the oxindole 21a with the same configuration about the spiro juncture at C(7) as the Alstonia oxindole alstonisine (1) with 10:1 diastereoselectivity, whereas the oxindole 24a with the opposite configuration was obtained diastereoselectively in greater than 91% yield when ketone 14a was treated with osmium tetraoxide in the presence of quinuclidine ligands. This conversion was found to be almost completely diastereoselective (94% de) to give oxindole 24a when dihydroquinine 4-chlorobenzoate (DHQ-CLB) was employed as the ligand. Tranformation of the N-b-methyltetracyclic ketone 14b produced the oxindole 24b which also possessed the configuration opposite to that of alstonisine (1) at the spirocyclic carbon [C(7)] under all reaction conditions investigated to date. Oxindoles 24a and 24b can be employed for the enantiospecific preparation of Gardneria and Voacanga oxindole bases. In addition, oxindole 21a is now available for the enantiospecific synthesis of Alstonia oxindole alkaloids.
• General approach for the synthesis of macroline/sarpagine related indole alkaloids via the asymmetric Pictet-Spengler reaction: The enantiospecific synthesis of (−)-anhydromacrosalhine-methine
  作者：Tong Gan、James M. Cook

  DOI：10.1016/0040-4039(96)01009-x

  日期：1996.7

  An enantiospecific total synthesis of (−)-anhydromacrosalhine-methine 3a has been accomplished from D-(+)-tryptophan via the asymmetric Pictet-Spengler reaction. A partial synthesis of 3a from the natural product (+)-ajmaline has also been completed.

  通过不对称的Pictet-Spengler反应，由D-（+）-色氨酸完成了对映体的（-）-脱水甲基甲硫氨酸-次甲基3a的全合成。还已经完成了从天然产物（+）-ajmaline的3a部分合成。