2-<2,2-bis(methylthio)ethyl>-4β-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole | 128948-93-6

• 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: 2-<2,2-bis(methylthio)ethyl>-4β-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole
• 英文别名: 2-(2,2-bis(methylthio)ethyl)-4β-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino[4,3-b]indole；(1S,12R,13S)-15-[2,2-bis(methylsulfanyl)ethyl]-13-ethyl-9,15-diazatetracyclo[10.3.1.02,10.03,8]hexadeca-2(10),3,5,7-tetraene
• CAS: 128948-93-6
• 化学式: C₂₀H₂₈N₂S₂
• 分子量: 360.588
• InChiKey: AHLKXGMXTBUXPO-GLJUWKHASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.17
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  19.03
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2-<2,2-bis(methylthio)ethyl>-4β-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole 在 Raney Ni (W-2) 、 dimethyl(methylthio)sulfonium tetrafluoroborate 、 sodium hydride 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 为溶剂， 反应 6.75h， 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 、 氢气 、 sodium carbonate 作用下， 以 1,4-二氧六环 、 甲醇 、 二氯甲烷 为溶剂， 反应 65.0h， 生成 2-<2,2-bis(methylthio)ethyl>-4β-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole
  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

• Dimethyl(methylthio)sulfonium fluoroborate induced cyclization of dithioacetals upon 2,3-disubstituted indoles
  作者：Mercedes Amat、Mercedes Alvarez、Josep Bonjoch、Núria Casamitjana、Jordi Gràcia、Rodolfo Lavilla、Xavier Garcías、Joan Bosch

  DOI：10.1016/s0040-4039(00)97420-3

  日期：1990.1

  Treatment of dithioacetals 1a–c, 3, and 4 with DMTSF accomplishes cyclization upon the indole 3-position to give the Strychnos-type pentacles 2a–c, 10, and 11, respectively.

  用DMTSF处理二硫缩醛1a-c，3和4可以在吲哚3位完成环化反应，分别得到Strychnos型五齿2a-c，10和11。
• Nucleophilic addition of indole-2-acetic ester enolates to N-alkylpyridinium salts. A formal synthesis of the strychnos alkaloids tubifolidine and tubifoline
  作者：Mercades Alvarez、Marisa Salas、Anna de Veciana、Rodolfo Lavilla、Joan Bosch

  DOI：10.1016/s0040-4039(00)97813-4

  日期：1990.1

  An efficient route for the synthesis of tetracyclic ABCD ring substructures of Strychnos alkaloids that incorporate the C-16 oxidized one-carbon substituent characteristic of the curan series and a formal synthesis of the nor-curan type alkaloids tubifolidine and tubifoline is reported.

  报告了一种合成马兜铃生物碱的四环ABCD环亚结构的有效途径，该结构结合了curan系列的C-16氧化的一碳取代基以及nor-curan型生物碱tubifolidine和tubifoline的形式合成。
• AMAT, MERCEDES;ALVAREZ, MERCEDES;BONJOCH, JOSEP;CASAMITJANA, NURIA;GRACIA+, TETRANEDRON LETT., 31,(1990) N4, C. 3453-3456
  作者：AMAT, MERCEDES、ALVAREZ, MERCEDES、BONJOCH, JOSEP、CASAMITJANA, NURIA、GRACIA+

  DOI：——

  日期：——
• ALVAREZ, MERCEDES;SALAS, MARISA;DE, VECIANA ANNA;LAVILLA, RODOLFO;BOSCH, +, TETRAHEDRON LETT., 31,(1990) N5, C. 5089-5092
  作者：ALVAREZ, MERCEDES、SALAS, MARISA、DE, VECIANA ANNA、LAVILLA, RODOLFO、BOSCH, +

  DOI：——

  日期：——
• AMAT, MERCEDES;LINARES, ANA;SALAS, M. -LUISA;ALVAREZ, MERCEDES;BOSCH, JOA+, J. CHEM. SOC. CHEM. COMMUN.,(1988) N 6, 420-421
  作者：AMAT, MERCEDES、LINARES, ANA、SALAS, M. -LUISA、ALVAREZ, MERCEDES、BOSCH, JOA+

  DOI：——

  日期：——