钩藤碱 C | 5629-60-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 中文名称: 钩藤碱 C
• 中文别名: 钩藤碱C
• 英文名称: pteropodine
• 英文别名: uncarine C；Pteropodin；methyl (1S,4aS,5aS,6R,10aS)-1-methyl-2'-oxospiro[1,4a,5,5a,7,8,10,10a-octahydropyrano[3,4-f]indolizine-6,3'-1H-indole]-4-carboxylate
• CAS: 5629-60-7
• 化学式: C₂₁H₂₄N₂O₄
• 分子量: 368.433
• InChiKey: JMIAZDVHNCCPDM-QLMFUGSGSA-N

物化性质

• 熔点：
  217-219℃
• 密度：
  1.33±0.1 g/cm3 (20 ºC 760 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  67.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  钩藤碱 C 在 盐酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 钩藤碱e
  参考文献：
  名称：

  吲哚生物碱的转化——Ⅰ：羟吲哚生物碱转化为吲哚生物碱

  摘要：

  已通过一系列反应将一些天然的羟吲哚（蝶呤，异氟哌啶和异羟胆碱）化学转化为相应的吲哚生物碱，这些反应包括用Meerwein's试剂形成天然羟吲哚的亚氨基醚，将亚氨基醚还原为2,3-氨基吲哚和2，3-二氨基吲哚环化成所需的天然吲哚生物碱。发现在乙酸中的硼氢化钠是用于将羟吲哚-亚氨基醚还原为2,3-癸二吲哚的特定试剂，它们是这些转化的关键中间体。育亨宾-羟吲哚亚氨基醚类似地转化为育亨宾和假育亨宾。获得了许多副产物，并阐明了它们的结构。

  DOI：

  10.1016/0040-4020(73)80138-3
• 作为产物：
  描述：

  4,9-二氢-3H-吡啶并(3,4-B)吲哚 在 甲醇 、 高氯酸 、 2,6-二叔丁基-4-甲基吡啶 、 次氯酸叔丁酯 、 aluminium hydride 、 silver perchlorate 、 sodium cyanoborohydride 、 溶剂黄146 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 均三甲苯 为溶剂， 反应 120.58h， 生成 钩藤碱 C
  参考文献：
  名称：

  Unified strategy for synthesis of indole and 2-oxindole alkaloids

  摘要：

  A concise and general entry to representative indole alkaloids of the yohimboid, heteroyohimboid, corynantheoid, and 2-oxindole classes has been developed exploiting a strategy that features intramolecular Diels-Alder reactions for the facile construction of the D/E ring subunits of the target alkaloids. The efficacy of the approach is first illustrated by a two-step total synthesis of the yohimboid alkaloid oxogambirtannine (2) from 22. Thus, the Diels-Alder substrate 25, which was prepared by nucleophilic addition of vinyl ketene acetal 24 to the intermediate N-acyliminium salt formed in situ upon reaction of 22 with 23, was heated in the presence of benzoquinone to give a mixture of diastereoisomeric cycloadducts 26 and 27; these adducts underwent spontaneous oxidation to furnish 2. In another application of the strategy, the [4 + 2] heterocyclization of 34a, which was formed upon nucleophilic addition of 1-[(trimethylsilyl)oxy]butadiene to the N-acyliminium salt generated in situ upon treatment of 22 with crotonyl chloride, afforded a mixture (ca. 9:1) of cycloadducts 35a and 36a. The major adduct 35a was converted to 42a using a general procedure for effecting beta-carbomethoxylation of enol ethers to give vinylogous carbonates. Subsequent reduction of 42a to the heteroyohimboid alkaloids (+/-)-tetrahydroalstonine (3) and (+/-)-cathenamine (4) was achieved by selective delivery of 2 or 1 equiv of hydride, respectively. When 42a was treated with sodium amide, stereoselective beta-elimination ensued to give 49, which was converted by chemoselective hydride reduction into the corynantheoid alkaloid (+/-)-geissoschizine (5). Facile access to alkaloids of the 2-oxindole family was realized by using a new protocol for achieving stereoselective, oxidative rearrangements of beta-carboline N(b) lactams into 3,3-disubstituted 2-oxindoles. Thus, exposure of 42a to tert-butyl hypochlorite followed by acid and silver ion induced rearrangement of the intermediate 3-chloroindolenine gave 50, with only traces of the C(7) epimer being detected. Hydride reduction of 50 gave (+/-)-isopteropodine (6), acid-catalyzed isomerization of which furnished an equilibrium mixture (1:3) of 6 and (+/-)-pteropodine (51). The stereochemical course of the intramolecular hetero-Diels-Alder reaction of 34a to give 35a and 36a as the only isolable cycloadducts was examined by computational analysis. The geometry of the six-atom transition state was established by semiempirical methods by using the standard closed-shell, restricted Hartree-Fock (RHF) version of the AM1 method. With use of this constrained geometry for the six-membered pericyclic array, the overall conformational energies for the four possible transition states 52-55 were minimized by MM2 calculations (MacroModel). The calculated relative energies of these transition states were in the order 52 < 53 < 54 < 55. Since the cyclization of 34a produced only 35a and 36a in an approximately 9:1 ratio via the respective transition states 52 and 53, these calculations correlated qualitatively with the experimental results.

  DOI：

  10.1021/ja00016a036

文献信息

• Analysis of the kinetics of isomerization of spiro oxindole alkaloids
  作者：Gerhard Laus、Dagmar Brössner、Gilbert Senn、Klaus Wurst

  DOI：10.1039/p29960001931

  日期：——

  The isomerization of the spiro oxindole alkaloids mitraphylline, isomitraphylline, pteropodine, isopteropodine, speciophylline and uncarine F in water has been studied at several temperatures and the rate coefficients have been determined. The effect of pH on the rate of reaction and the equilibrium composition has been investigated. The rate coefficients in water and in organic solvents correlate

  螺环羟吲哚生物碱米茶碱，异吗啉茶碱，翼蛇毒碱，异蝶足碱，茶碱茶碱和胭脂红F的异构化已在数个温度下进行了研究，并确定了速率系数。已经研究了pH对反应速率和平衡组成的影响。水和有机溶剂中的速率系数与Dimroth–Reichardt溶剂极性参数令人满意地相关。目前的结果支持极性溶剂稳定的两性离子中间体的存在，并表明生物碱的质子化抑制了异构化。已经确定了翼手足的晶体结构。
• Kinetics of acetonitrile-assisted oxidation of tertiary amines by hydrogen peroxide
  作者：Gerhard Laus

  DOI：10.1039/b102066h

  日期：——

  The rate of oxidation of tertiary amines by aqueous hydrogen peroxide is increased in the presence of acetonitrile due to the formation of a reactive intermediate. The active oxidant, presumably peroxyacetimidic acid, was quantified by a photometric method. Activation parameters of the acetonitrile-assisted and non-assisted oxidations are given in the temperature range 20 to 40 °C. The increased rate of the assisted oxidation is explained by the low enthalpy of activation although the entropy of activation is more negative due to a highly ordered transition state.

  过氧化氢水溶液氧化叔胺的速率在有乙腈存在的情况下会增加，这是由于形成了一种活性中间体。活性氧化剂（可能是过氧乙酰亚氨酸）用光度法进行了定量。给出了乙腈辅助氧化和非辅助氧化在 20 至 40 °C 温度范围内的活化参数。虽然由于过渡态高度有序，活化熵为负值，但活化焓较低，这解释了辅助氧化速率增加的原因。
• New methods for the synthesis of oxindole alkaloids. Total syntheses of isopteropodine and pteropodine.
  作者：Stephen F. Martin、Michael Mortimore

  DOI：10.1016/s0040-4039(00)97675-5

  日期：1990.1

  The 2-oxindole alkaloids isopteropodine (11) and pteropodine (12) were conveniently synthesised from the known pentacycle (9) via a new and general protocol for oxidation and rearrangement of carboline lactams into 3,3-disubstituted-2-oxindoles.

  通过已知的五环化合物（9）通过新的通用方案将羰基内酰胺氧化和重排为3,3-二取代-2-氧吲哚，可以方便地从已知的五环（9）合成2-oxindole生物碱异蝶足碱（11）和ptepopodine（12）。
• Montenegro de Matta; Delle Monache; Ferrari, Farmaco, Edizione Scientifica, 1976, vol. 31, # 7, p. 527 - 535
  作者：Montenegro de Matta、Delle Monache、Ferrari、MariniBettolo

  DOI：——

  日期：——
• MARTIN, STEPHEN E.;MORTIMORE, MICHAEL, TETRAHEDRON LETT., 31,(1990) N7, C. 4557-4560
  作者：MARTIN, STEPHEN E.、MORTIMORE, MICHAEL

  DOI：——

  日期：——