<3S*-(3α,15α,16β)>-1,3,5,6,14,15,16,17-Octahydro-16-acetyl-15-<(methoxycarbonyl)methyl>indolo<2,3-a>quinolizine | 93600-89-6

• 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: <3S*-(3α,15α,16β)>-1,3,5,6,14,15,16,17-Octahydro-16-acetyl-15-<(methoxycarbonyl)methyl>indolo<2,3-a>quinolizine
• 英文别名: methyl 2-[(2R,3R,12bS)-3-acetyl-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a]quinolizin-2-yl]acetate
• CAS: 93600-89-6
• 化学式: C₂₀H₂₄N₂O₃
• 分子量: 340.422
• InChiKey: JRNNDSSMOWKMSK-QBIMZIAESA-N

物化性质

• 沸点：
  511.1±50.0 °C(predicted)
• 密度：
  1.26±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  62.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  <3S*-(3α,15α,16β)>-1,3,5,6,14,15,16,17-Octahydro-16-acetyl-15-<(methoxycarbonyl)methyl>indolo<2,3-a>quinolizine 在 sodium tetrahydroborate 作用下， 生成 19α-methyl-18-oxa-yohimban-17-one
  参考文献：
  名称：

  由（-）-色氨酸合成（-）-尿嘧啶

  摘要：

  （–）-色氨酸经过15步转化为（–）-ajmalicine；关键步骤是分子内迈克尔反应，其中C（15）–C（20）键在完全立体控制的情况下形成。

  DOI：

  10.1039/c39840000715
• 作为产物：
  描述：

  N-亚苄基-2-(1H-吲哚-3-基)乙胺 在 palladium on activated charcoal 四氢吡咯 、 sodium hydroxide 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 正丁基锂 、 氢气 、 三乙胺 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 溶剂黄146 、 丙酮 为溶剂， -78.0~20.0 ℃ 、110.0 kPa 条件下， 反应 21.5h， 生成 <3S*-(3α,15α,16β)>-1,3,5,6,14,15,16,17-Octahydro-16-acetyl-15-<(methoxycarbonyl)methyl>indolo<2,3-a>quinolizine
  参考文献：
  名称：

  使用Wittig-Horner和Knoevenagel反应合成苦豆碱衍生物

  摘要：

  用五步步骤从色胺中合成的2-（2,3,4,9-四氢-1 H -β-咔啉-1-基）乙醛很容易通过Wittig-Horner或Knoevenagel反应同化为取代的丙烯酸酯。这些高反应性化合物是天然吲哚生物碱阿兹玛林类似物合成中的关键中间体。

  DOI：

  10.1016/s0040-4039(99)01921-8

文献信息

• Massiot, G., Bulletin des Societes Chimiques Belges, 1990, vol. 99, # 9, p. 717 - 728
  作者：Massiot, G.

  DOI：——

  日期：——
• Applications of Vinylogous Mannich Reactions. Asymmetric Synthesis of the Heteroyohimboid Alkaloids (-)-Ajmalicine, (+)-19-epi-Ajmalicine, and (-)-Tetrahydroalstonine
  作者：Stephen F. Martin、Cameron W. Clark、Jeffrey W. Corbett

  DOI：10.1021/jo00115a044

  日期：1995.5

  The vinylogous Mannich additions of 1-[(trialkylsilyl)oxy]butadienes to the acyl iminium salt derived from 7 proceeded with a modest degree of stereoselectivity to give a mixture (1.8:1) of 8 and 9. The triene 8 underwent an intramolecular hetero Diels-Alder reaction to give the pentacyclic intermediate 10. Decarboxylation of 10 according to the Barton protocol led to 13, which was then elaborated to (-)-tetrahydroalstonine (1) by a straightforward sequence of reactions. This asymmetric synthesis of 1 required only 10 steps from readily available L-tryptophan. On the other hand, the related vinylogous Mannich addition of a vinyl ketene acetals to 16 were highly stereoselective giving the corresponding trans-substituted hydrocarboline as the only detectable product. Subsequent reaction of this adduct with methyl vinyl ketone followed by cyclization of the intermediate 18 gave the key tetracyclic intermediate 19. Removal of the carboxyl group from the C(5) position of 19 following the Barton procedure gave the ketone 20, which was converted into (-)-ajmalicine (2) in three steps by a known procedure. Alternatively, hydride reduction of the tetracyclic amine 19 gave the alcohol 22, which was subjected to a modified Mitsunobu reaction; selective hydrolysis of the intermediate triester led to the lactone 24. Radical decarboxylation via the Barton procedure gave an intermediate lactone that was converted into (+)-19-epi-ajmalicine (3) in two steps. Removal of the carboxyl presented pathways to both (-)-ajmalicine (2) and (+)-19-epi-ajmalicine (3). Thus, the asymmetric syntheses of 2 and 3 were completed by concise sequences of reactions requiring only 11 and 13 steps, respectively, from D-tryptophan.
• Naito, Takeaki; Kojima, Noriko; Miyata, Okiko, Heterocycles, 1986, vol. 24, # 8, p. 2117 - 2120
  作者：Naito, Takeaki、Kojima, Noriko、Miyata, Okiko、Ninomiya, Ichiya

  DOI：——

  日期：——
• Synthesis of ajmalicine derivatives using Wittig-Horner and Knoevenagel reactions
  作者：Ahcène Boumendjel、Jean-Marc Nuzillard、Georges Massiot

  DOI：10.1016/s0040-4039(99)01921-8

  日期：1999.12

  2-(2,3,4,9-Tetrahydro-1H-β-carbolin-1-yl)acetaldehyde, synthesized from tryptamine in five steps, is easily homologated by Wittig-Horner or Knoevenagel reactions to substituted acrylates. These highly reactive compounds are key intermediates in the synthesis of analogs of the natural indol alkaloid ajmalicine.

  用五步步骤从色胺中合成的2-（2,3,4,9-四氢-1 H -β-咔啉-1-基）乙醛很容易通过Wittig-Horner或Knoevenagel反应同化为取代的丙烯酸酯。这些高反应性化合物是天然吲哚生物碱阿兹玛林类似物合成中的关键中间体。
• Synthesis of (–)-ajmalicine from (–)-tryptophan
  作者：Georges Massiot、Tshilundu Mulamba

  DOI：10.1039/c39840000715

  日期：——

  (–)-Tryptophan has been converted into(–)-ajmalicine in 15 steps; the key step is an intramolecular Michael reaction in which the C(15)–C(20) bond is formed with full stereocontrol.

  （–）-色氨酸经过15步转化为（–）-ajmalicine；关键步骤是分子内迈克尔反应，其中C（15）–C（20）键在完全立体控制的情况下形成。