methyl 2,16-didehydro-6α-(methylthio)tubifolidine-1-carboxylate | 122419-45-8

• 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: methyl 2,16-didehydro-6α-(methylthio)tubifolidine-1-carboxylate
• CAS: 122419-45-8
• 化学式: C₂₁H₂₆N₂O₂S
• 分子量: 370.516
• InChiKey: WKKDIZKXLHYRRX-UCGXPTDZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.87
• 重原子数：
  26.0
• 可旋转键数：
  2.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  32.78
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  methyl 2,16-didehydro-6α-(methylthio)tubifolidine-1-carboxylate 在 Raney Ni (W-2) 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 2.5h， 生成 (-)-19,20-dihydroakuammicine
  参考文献：
  名称：

  A new synthetic entry to pentacyclic Strychnos alkaloids. Total synthesis of (.+-.)-tubifolidine, (.+-.)-tubifoline, and (.+-.)-19,20-dihydroakuammicine

  摘要：

  A new strategy for the synthesis of pentacyclic Strychnos alkaloids has been developed. It consists in the closure of the five-membered E ring by cyclization upon the indole 3-position from a suitably N-substituted tetracyclic system embodying rings ABCD of the alkaloids. Attempts to effect the key cyclization either by Pummerer rearrangement of sulfinylacetamides 4 and 6, from chloroacetamide 12, or from bis(methylthio)acetamide 10b (exocyclic amide carbonyl group) resulted in failure. In the first case dithioacetals 9 and 10, respectively, were formed in good yields. Cyclization from alcohol 13 or from the indole-deactivated acetal 15 and dithiocetal 18 were also unsuccessful: noncyclized products coming from the initially formed oxonium or thionium intermediates 16 were obtained. Cyclization was satisfactorily accomplished in 49% yield by treatment of the N-unsubstituted indole dithioacetal 23 with DMTSF. The resulting pentacycle 25 was converted to 20-deethyltubifolidine (27). A similar treatment from dithioacetal 41a, prepared from the secondary amine 32a, afforded pentacycle 42a, from which the alkaloids tubifoline, tubifolidine, and 19,20-dihydroakuammicine were synthesized.

  DOI：

  10.1021/jo00313a017
• 作为产物：
  描述：

  (1RS, 4RS, 5SR)-2-benzyl-4-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole 在 palladium dihydroxide 三氟化硼乙醚 、 dimethyl(methylthio)sulfonium tetrafluoroborate 、 氢气 、 sodium hydride 、 sodium carbonate 作用下， 以 1,4-二氧六环 、 甲醇 、 二氯甲烷 为溶剂， 反应 69.25h， 生成 methyl 2,16-didehydro-6α-(methylthio)tubifolidine-1-carboxylate
  参考文献：
  名称：

  A new synthetic entry to pentacyclic Strychnos alkaloids. Total synthesis of (.+-.)-tubifolidine, (.+-.)-tubifoline, and (.+-.)-19,20-dihydroakuammicine

  摘要：

  A new strategy for the synthesis of pentacyclic Strychnos alkaloids has been developed. It consists in the closure of the five-membered E ring by cyclization upon the indole 3-position from a suitably N-substituted tetracyclic system embodying rings ABCD of the alkaloids. Attempts to effect the key cyclization either by Pummerer rearrangement of sulfinylacetamides 4 and 6, from chloroacetamide 12, or from bis(methylthio)acetamide 10b (exocyclic amide carbonyl group) resulted in failure. In the first case dithioacetals 9 and 10, respectively, were formed in good yields. Cyclization from alcohol 13 or from the indole-deactivated acetal 15 and dithiocetal 18 were also unsuccessful: noncyclized products coming from the initially formed oxonium or thionium intermediates 16 were obtained. Cyclization was satisfactorily accomplished in 49% yield by treatment of the N-unsubstituted indole dithioacetal 23 with DMTSF. The resulting pentacycle 25 was converted to 20-deethyltubifolidine (27). A similar treatment from dithioacetal 41a, prepared from the secondary amine 32a, afforded pentacycle 42a, from which the alkaloids tubifoline, tubifolidine, and 19,20-dihydroakuammicine were synthesized.

  DOI：

  10.1021/jo00313a017

文献信息

• Synthesis and nmr data of the strychnos indole alkaloid tubifoline
  作者：Mercedes Amat、Ana Linares、Javier Muñoz、Joan Bosch

  DOI：10.1016/s0040-4039(00)82350-3

  日期：1988.1

  The total synthesis of the Strychnos indole alkaloid tubifoline and detailed 1H- and 13C-NMR data of this alkaloid are reported.

  所述的全合成马钱子吲哚生物碱tubifoline和详细1 H-和13生物碱报道的该C-NMR的数据。