methyl (+/-)-(E)-4-<2,3,4,9-tetrahydro-2-<(2-oxo-2H-pyran-6-yl)carbonyl>-1H-pyrido<3,4-b>indol-1-yl>-2-butenoate | 122908-73-0

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 哈马拉生物碱
• 英文名称: methyl (+/-)-(E)-4-<2,3,4,9-tetrahydro-2-<(2-oxo-2H-pyran-6-yl)carbonyl>-1H-pyrido<3,4-b>indol-1-yl>-2-butenoate
• 英文别名: methyl (E)-4-[2-(6-oxopyran-2-carbonyl)-1,3,4,9-tetrahydropyrido[3,4-b]indol-1-yl]but-2-enoate
• CAS: 122908-73-0
• 化学式: C₂₂H₂₀N₂O₅
• 分子量: 392.411
• InChiKey: GIQUCAMIPOQIES-ONNFQVAWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  88.7
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (+/-)-(E)-4-<2,3,4,9-tetrahydro-2-<(2-oxo-2H-pyran-6-yl)carbonyl>-1H-pyrido<3,4-b>indol-1-yl>-2-butenoate 在 对苯醌 作用下， 以 various solvent(s) 为溶剂， 反应 48.0h， 以91%的产率得到oxogambirtannine
  参考文献：
  名称：

  分子内Diels-Alder反应的芳香族育亨宾类和原小ber碱生物碱的简便方法

  摘要：

  通过取代的β-咔啉13的分子内[4 + 2]环加成/脱氢反应，高收率合成了芳香族育亨宾吲哚生物碱oxambiambirtannine（9），在存在的情况下10与酰基氯11的反应很容易获得。二烯12。以类似的方式，在取代异喹啉17环化后，快速构建原型小ber碱骨架20。

  DOI：

  10.1016/s0040-4039(00)82439-9
• 作为产物：
  描述：

  2-氧代-2H-吡喃-6-甲酰氯 、 4,9-二氢-3H-吡啶并(3,4-B)吲哚 、 tert-butyl(((E)-1-methoxybuta-1,3-dien-1-yl)oxy)dimethylsilane 以 四氢呋喃 为溶剂， 以86%的产率得到methyl (+/-)-(E)-4-<2,3,4,9-tetrahydro-2-<(2-oxo-2H-pyran-6-yl)carbonyl>-1H-pyrido<3,4-b>indol-1-yl>-2-butenoate
  参考文献：
  名称：

  分子内Diels-Alder反应的芳香族育亨宾类和原小ber碱生物碱的简便方法

  摘要：

  通过取代的β-咔啉13的分子内[4 + 2]环加成/脱氢反应，高收率合成了芳香族育亨宾吲哚生物碱oxambiambirtannine（9），在存在的情况下10与酰基氯11的反应很容易获得。二烯12。以类似的方式，在取代异喹啉17环化后，快速构建原型小ber碱骨架20。

  DOI：

  10.1016/s0040-4039(00)82439-9

文献信息

• Unified strategy for synthesis of indole and 2-oxindole alkaloids
  作者：Stephen F. Martin、James E. Hunter、Brigitte Benage、Leo S. Geraci、Michael Mortimore

  DOI：10.1021/ja00016a036

  日期：1991.7

  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.
• MARTIN, STEPHEN F.;BENAGE, BRIGITTE;GERACI, LEO S.;HUNTER, JAMES E.;MORTI+, J. AMER. CHEM. SOC., 113,(1991) N6, C. 6161-6171
  作者：MARTIN, STEPHEN F.、BENAGE, BRIGITTE、GERACI, LEO S.、HUNTER, JAMES E.、MORTI+

  DOI：——

  日期：——