(-)-serratoline | 74260-86-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉类
• 英文名称: (-)-serratoline
• 英文别名: serratoline；Daamnimkdzashk-vslccporsa-；(1R,10R,12R,15S,17S)-1,14,14-trimethyl-3,13-diazapentacyclo[13.2.2.02,10.04,9.012,17]nonadeca-2,4,6,8-tetraen-10-ol
• CAS: 74260-86-9
• 化学式: C₂₀H₂₆N₂O
• 分子量: 310.439
• InChiKey: DAAMNIMKDZASHK-VSLCCPORSA-N

物化性质

• 沸点：
  449.7±45.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  44.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-serratoline 在 sodium tetrahydroborate 、 间氯过氧苯甲酸 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 水 、 三氟乙酸 为溶剂， 反应 30.12h， 生成 3-epialloseratoline
  参考文献：
  名称：

  合成Aristotelia -Type生物碱。第十二部分。（-）-tasmanine的全合成。控制3 H-吲哚-3-醇衍生物重排至羟吲哚（= 1,3-二氢-2 H-吲哚-2-ones）或拟吲哚酚（= 1,2-二氢-3 H-吲哚）的立体电子因素-3-ones）†

  摘要：

  （+）-马兜铃啉（（+）- 5）的氧化转化为代谢产物，即最近合成的吲哚生物碱（-）-塞拉托林（（-）- 6），（+）-马兜铃酮（（+）- 2） ，和（-）-别石蒜碱（（-）- 22），进行了更详细的研究。已经证明，（+）- 5与3-氯过苯甲酸的反应的非对映体选择性可以通过改变溶剂以及通过添加CF 3 COOH来改变。中间体3 H-吲哚-3-醇衍生物的1,2-重排的化学选择性可通过以下方式控制：3 H的处理-吲哚-3-醇与多磷酸水溶液可生成假吲哚基（= 1,2-二氢-3 H-吲哚-3-酮）衍生物，而对相应的O-苯甲酸酯的类似处理仅提供了相应的结构异构2-氧吲哚（＝ 1，3-二氢-2 H-吲哚-2-一）产物。导致的有效全合成的这些和相关的研究结果开发Aristotelia生物碱（ - ） - tasmanine（（ - ） - 1）和相应的非天然差向异构体的（+） - 12，以及两个pseudoindoxyls的（+）

  DOI：

  10.1002/hlca.19930760505
• 作为产物：
  描述：

  (+)-aristotelone 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 624.0h， 以62%的产率得到(-)-serratoline
  参考文献：
  名称：

  A stereoselective transformation of pseudoindoxyls into oxindoles in a single operation

  摘要：

  The Aristotelia alkaloid (+)-aristotelone (1), a spiro-pseudoindoxyl derivative, is transformed in over 90 % yield into the oxindole (+)-3-epitasmanine (3) upon treatment with hot BF3.Et(2)O in CH2Cl2. This intriguing transformation possibly proceeds through the intermediate 3-hydroxyindolenine derivative (-)-serratoline (2) which could be isolated when the reaction was run under milder conditions. This rearrangement, for which there is little precedent, is highly stereoselective in that the lactam carbonyl group ends up on the same face of the molecule as the C=O-unit of the starting pseudoindoxyl. That this outcome is due to a kinetic control was demonstrated by showing that the epimeric starting material (-)-4 furnished exclusively the naturally occurring alkaloid (-)-tasmanine (5) under the same reaction conditions.

  DOI：

  10.1016/s0040-4039(00)75984-3

文献信息

• Synthesis of<i>Aristotelia</i>-Type Alkaloids. Part XIII. Total syntheses of (+)-makonine, (+)-aristotelinone, and (+)-11,12-didehydroaristoteline
  作者：Reto Stahl、Renato Galli、Rolf Güller、Hans-Jürg Borschberg

  DOI：10.1002/hlca.19940770805

  日期：1994.12.14

  (+)-aristoteline ((+)-6) into other metabolites which had been isolated from Aristotelia species was investigated. Thus, treatment of (+)-6 with I2 as the single oxidant furnished the naturally occurring indole alkaloids (+)-makonine ((+)-9),(+)-aristotelinone ((+)-11), or (+)-11, 12-didehydroaristoteline ((+)-7) in good yields, the selectivity of the oxidation process depending on the chosen reaction conditions.

  研究了合成的（+）-马兜铃啉（（+）- 6）氧化转化成其他代谢物的过程，这些代谢物已从亚里斯多德氏菌属物种中分离出来。因此，用I 2作为单一氧化剂对（+）- 6的处理提供了天然存在的吲哚生物碱（+）-酮可宁（（+）- 9），（+）-马兜铃酮（（+）- 11）或（ +）-11，12-二氢氢化马兜铃啉（（+）- 7）收率高，氧化过程的选择性取决于所选的反应条件。
• Synthesis of aristotelia-type alkaloids. Part X. Biomimetic transformation of synthetic (+)-aristoteline into (−)-alloaristoteline.
  作者：Rolf Güller、Hans-Jürg Borschberg

  DOI：10.1016/s0957-4166(00)82105-9

  日期：1992.9

  inverted indole moiety. The first intermediate along this route turned out to be identical with natural (−)-serratoline (5), and a rearrangement product thereof corresponded to (+)-aristotelone (6), an alkaloid that has been isolated by others from Aristotelia chilensis in 1976. Our investigations unambiguously confirmed the tentative structure of this metabolite, which is endowed with a spiro[4.4]nonane-3-oxindole

  合成（+） - aristoteline（2）转化到（ - ） - alloaristoteline（1）在4个步骤86％的总产率。这种成功的仿生互变建立了这种不寻常的天然产物的先前未知的绝对构型，其中该天然产物含有一个反向的吲哚部分。沿这条路线的第一中间体与天然（-）-erratoline（5）相同，其重排产物对应于（+）-aristotelone（6），这是一种生物碱，已被其他人从Aristotelia chilensis分离出。 1976年。我们的研究明确证实了这种代谢产物的暂定结构，该结构具有螺环[4.4]壬烷-3-氧吲哚亚基。
• Total synthesis of (-)-alloaristoteline, (-)-serratoline, and (+)-aristotelone
  作者：Doris Stoermer、Clayton H. Heathcock

  DOI：10.1021/jo00055a007

  日期：1993.1

  The Aristotelia alkaloids (-)-alloaristoteline (4), (-)-serratoline (12), and (+)-aristotelone (13) have been prepared as summarized in Scheme IV. Thus, via the method of Stevens, (1S)-(-)-beta-pinene (9) and 3-indolylacetonitrile (10) were coupled by a Hg(NO3)2-mediated Ritter reaction followed by reduction of the resulting imine to give (+)-makomakine (11). An intramolecular Friedel-Crafts reaction delivered (+)-aristoteline (3), which was oxidized by reaction with oxygen and platinum. Reduction of the intermediate hydroperoxide delivered alkaloid 12. Base-catalyzed skeletal rearrangement of 12 provided alkaloid 13, which was reduced with LiAlH4 to obtain a mixture of secondary alcohols, 14a,b. Treatment of each of these alcohols with HCI in methanol afforded (-)-alloaristoteline (4).
• Synthesis of Aristotelia-Type Alkaloids. Part XII. Total synthesis of (−)-tasmanine. Stereoelectronic factors that control the rearrangement of 3H-indol-3-ol derivatives to oxindoles ( = 1,3-dihydro-2H-indol-2-ones) or to pseudoindoxyls ( =1,2-dihydro-3H-
  作者：Rolf Güller、Hans-Jürg Borschberg

  DOI：10.1002/hlca.19930760505

  日期：1993.8.11

  The oxidative transformation of (+)-aristoteline ((+)-5) into its metabolites, the recently synthesized indole alkaloids (−)-serratoline ((−)-6), (+)-aristotelone ((+)-2), and (−)-alloaristoteline ((−)-22), was investigated in more detail. It was demonstrated that the diastereoface selectivity of the reaction of (+)-5 with 3-chloroperbenzoic acid can be altered by variation of the solvent as well as

  （+）-马兜铃啉（（+）- 5）的氧化转化为代谢产物，即最近合成的吲哚生物碱（-）-塞拉托林（（-）- 6），（+）-马兜铃酮（（+）- 2） ，和（-）-别石蒜碱（（-）- 22），进行了更详细的研究。已经证明，（+）- 5与3-氯过苯甲酸的反应的非对映体选择性可以通过改变溶剂以及通过添加CF 3 COOH来改变。中间体3 H-吲哚-3-醇衍生物的1,2-重排的化学选择性可通过以下方式控制：3 H的处理-吲哚-3-醇与多磷酸水溶液可生成假吲哚基（= 1,2-二氢-3 H-吲哚-3-酮）衍生物，而对相应的O-苯甲酸酯的类似处理仅提供了相应的结构异构2-氧吲哚（＝ 1，3-二氢-2 H-吲哚-2-一）产物。导致的有效全合成的这些和相关的研究结果开发Aristotelia生物碱（ - ） - tasmanine（（ - ） - 1）和相应的非天然差向异构体的（+） - 12，以及两个pseudoindoxyls的（+）
• A stereoselective transformation of pseudoindoxyls into oxindoles in a single operation
  作者：Rolf Güller、Hans-Jürg Borschberg

  DOI：10.1016/s0040-4039(00)75984-3

  日期：1994.1

  The Aristotelia alkaloid (+)-aristotelone (1), a spiro-pseudoindoxyl derivative, is transformed in over 90 % yield into the oxindole (+)-3-epitasmanine (3) upon treatment with hot BF3.Et(2)O in CH2Cl2. This intriguing transformation possibly proceeds through the intermediate 3-hydroxyindolenine derivative (-)-serratoline (2) which could be isolated when the reaction was run under milder conditions. This rearrangement, for which there is little precedent, is highly stereoselective in that the lactam carbonyl group ends up on the same face of the molecule as the C=O-unit of the starting pseudoindoxyl. That this outcome is due to a kinetic control was demonstrated by showing that the epimeric starting material (-)-4 furnished exclusively the naturally occurring alkaloid (-)-tasmanine (5) under the same reaction conditions.