(+/-)-tabersonine | 21217-98-1

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 鸡蛋花型生物碱
• 英文名称: (+/-)-tabersonine
• 英文别名: tabersonine；methyl (1S,12S,19R)-12-ethyl-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,9,13-pentaene-10-carboxylate
• CAS: 21217-98-1
• 化学式: C₂₁H₂₄N₂O₂
• 分子量: 336.434
• InChiKey: FNGGIPWAZSFKCN-NJDAHSKKSA-N

物化性质

• 沸点：
  488.7±45.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  41.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (o-nitrophenyl)phenyliodonium iodide 在 titanium(III) chloride 、 碘代三甲硅烷 、 potassium tert-butylate 、 ammonium acetate 、 silver fluoride 、 sodium carbonate 、 甲基磺酰氯 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 二甲基亚砜 为溶剂， 生成 (+/-)-tabersonine
  参考文献：
  名称：

  A General Strategy to Aspidosperma Alkaloids:  Efficient, Stereocontrolled Synthesis of Tabersonine

  摘要：

  DOI：

  10.1021/ja983198k

文献信息

• An Efficient Approach to <i>Aspidosperma </i>Alkaloids via [4 + 2] Cycloadditions of Aminosiloxydienes:  Stereocontrolled Total Synthesis of (±)-Tabersonine. Gram-Scale Catalytic Asymmetric Syntheses of (+)-Tabersonine and (+)-16-Methoxytabersonine. Asymmetric Syntheses of (+)-Aspidospermidine and (−)-Quebrachamine
  作者：Sergey A. Kozmin、Tetsuo Iwama、Yong Huang、Viresh H. Rawal

  DOI：10.1021/ja017863s

  日期：2002.5.1

  readily adapted to the asymmetric synthesis of these compounds. The strategy is demonstrated by the total synthesis of (+/-)-tabersonine (rac-1), proceeding through a 12-step sequence. The basis for this approach was provided by a highly regio- and stereoselective [4 + 2] cycloaddition of 2-ethylacrolein with 1-amino-3-siloxydiene developed in our laboratory. Subsequent elaboration of the initial adduct

  描述了一种简洁、高度立体控制的吲哚生物碱 Aspidosperma 家族的策略，该策略很容易适应这些化合物的不对称合成。该策略由 (+/-)-tabersonine (rac-1) 的全合成证明，通过 12 步序列进行。这种方法的基础是我们实验室开发的 2-乙基丙烯醛与 1-氨基-3-甲硅烷氧基二烯的高度区域和立体选择性 [4 + 2] 环加成。随后通过闭环烯烃复分解反应有效地将初始加合物加工成六氢喹啉 DE 环系统。开发了烯醇甲硅烷基醚与（邻硝基苯基）苯基碘氟化物的新型邻硝基苯基化，以实现必要的吲哚部分的有效区域选择性引入。ABDE四环最终高产转化为五环目标rac-1依赖于分子内吲哚烷基化和区域选择性C-碳甲氧基化。我们的方法在战略上与以前的路线不同，并且包含访问 Aspidosperma 吲哚生物碱家族的许多其他成员所必需的内置灵活性。通过以下 Aspidosperma 生物碱的不对称
• 16-epi-19-S-vindolinine, an indoline alkaloid from Catharanthus roseus
  作者：Atta-ur-Rahman、M. Bashir、S. Kaleem、T. Fatima

  DOI：10.1016/0031-9422(83)85046-8

  日期：1983.1

  Abstract Studies on the alkaloids of Catharanthus roseus have resulted in the isolation of a new alkaloid, to which the structure of 16-epi-19-S-vindolinine has been assigned.

  摘要 对长春花生物碱的研究已分离出一种新的生物碱，其结构为 16-epi-19-S-vindolinine。
• Studies in biomimetic alkaloid syntheses. 8. Total syntheses of the C-14 epimeric hydroxyvincadifformines, tabersonine, a (hydroxymethyl)-D-norvincadifformine and the C-20 epimeric pandolines
  作者：Martin E. Kuehne、F. J. Okuniewicz、C. L. Kirkemo、J. C. Bohnert

  DOI：10.1021/jo00346a034

  日期：1982.3
• Synthesis of vinca alkaloids and related compounds. 63. A new synthetic pathway for preparing alkaloids and related compounds with the aspidosperma skeleton. Total syntheses of (.+-.)-vincadifformine, (.+-.)-tabersonine, and (.+-.)-oxotabersonine
  作者：Gyorgy Kalaus、Istvan Greiner、Maria Kajtar-Peredy、Janos Brlik、Lajos Szabo、Csaba Szantay

  DOI：10.1021/jo00058a025

  日期：1993.3

  Compound 3, which has an indole skeleton containing a masked acryl ester function, was synthesized from the hydrochloride of 2-(ethoxycarbonyl)tryptamine (2). The cycloaddition of 3 with methyl 4-formylhexanoate (21) or with 5-(benzoyloxy)-2-ethylpentanal (33) yielded the starting materials for target compounds (+/-)-vincadifformine (4), (+/-)-3-oxotabersonine (42), and (+/-)-tabersonine (43). The synthesis of vincadifformine (4) was achieved in two different ways: via 3-oxovincadifformine (7) and via tetracyclic benzoate esters 37 and 38. The double bond required in tabersonine (43) and 3-oxotabersonine (42) was introduced by treatment of 3-thioxovincadifformine (39) with p-toluenesulfinyl chloride.
• Total Syntheses of Vincadifformine, 3-Oxovincadifformine, Pseudo- and 20-<i>epi</i>-Pseudovincadifformine, Tabersonine, and Δ¹⁸-Tabersonine through Radical Reactions and Heck Reactions
  作者：Martin E. Kuehne、Tiansheng Wang、Pamela J. Seaton

  DOI：10.1021/jo960607r

  日期：1996.1.1

  The pentacyclic alkaloids vincadifformine (9), psi-vincadifformine (15), and epi-psi-vincadifformine (16) could be synthesized by intramolecular free-radical-induced cyclizations of the tetracyclic intermediates 7, 8, and 18, which were respectively obtained by condensation of the indoloazepine 1 with 2-(phenylselenyl)butyraldehyde and subsequent N-b-alkylation of the resulting tetracyclic amines 2 and 3, or from condensation of (phenylselenyl)acetaldehyde with the alkylated indoloazepine 17. The intermediates 2 and 3 also gave 3-oxovincadifformine (21) by an intermolecular radical alkylation with methyl acrylate. Their alkylation with (Z)-1,3-diiodopropene, phenyl selenoxide elimination, and intramolecular Heck reactions provided tabersonine (24) and 18,19-didehydrotabersonine (27).