methyl 2,16-didehydrotubifolidine-1-carboxylate | 122419-46-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 英文名称: methyl 2,16-didehydrotubifolidine-1-carboxylate
• 英文别名: methyl (1R,11S,12S,17S)-12-ethyl-8,14-diazapentacyclo[9.5.2.01,9.02,7.014,17]octadeca-2,4,6,9-tetraene-8-carboxylate
• CAS: 122419-46-9
• 化学式: C₂₀H₂₄N₂O₂
• 分子量: 324.423
• InChiKey: KSGZICMVJLHYKA-MJPMAJQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.53
• 重原子数：
  24.0
• 可旋转键数：
  1.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  32.78
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  methyl 2,16-didehydrotubifolidine-1-carboxylate 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以80%的产率得到(-)-tubifoline
  参考文献：
  名称：

  兜兰吲哚生物碱微粉碱的合成与核磁共振数据。

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(00)82350-3
• 作为产物：
  描述：

  methyl 1-benzyl-5-ethyl-2-(1H-indol-3-yl)piperidine-4-carboxylate 在 palladium dihydroxide barium dihydroxide 、 lithium aluminium tetrahydride 、 Raney Ni (W-2) 、 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 、 乙醇 、 二氯甲烷 为溶剂， 反应 112.75h， 生成 methyl 2,16-didehydrotubifolidine-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

• Total syntheses of the Strychnos indole alkaloids(−)-tubifoline, (−)-tubifolidine, and (−)-19,20-dihydroakuammicine
  作者：Mercedes Amat、M.-Dolors Coll、Joan Bosch、Enric Espinosa、Elies Molins

  DOI：10.1016/s0957-4166(97)00071-2

  日期：1997.3

  Two different stragies for the synthesis of pentacyclic Strychnos alkaloids in enantiomerically pure form are explored. Both of them involve the use of enantiopure 2-(4-piperidylmethyl)indoles prepared by kinetic resolution of 1-(3-pyridyl)ethanol, followed by partial reduction of the pyridine ring to the tetrahydropyridine level, Claisen rearrangement of the resulting allylic alcohol, and finally

  为五环的合成两种不同stragies马钱子生物碱在对映体纯的形式进行了探索。它们都涉及使用对映体纯的2-（4-哌啶基甲基）吲哚，其是通过动力学拆分1-（3-吡啶基）乙醇而制备的，然后将吡啶环部分还原成四氢吡啶水平，将所得的烯丙醇进行克莱森重排。 ，最后是史密斯的化身。而2-（4-哌啶基甲基）吲哚6不能转换到的四环ABDE子马钱子碱，氯乙酰胺的photocyclization 14，从（哌啶基甲基）吲哚衍生的13，令人满意地得到stemmadenine型四环15，然后将其转化为生物碱（-）-tubifoline，（-）-tubifolidine和（-）-19,20-dihydroakuammicine。
• First total synthesis and NMR data of the alkaloid 19,20-dihydroakuammicine
  作者：Mercedes Amat、Ana Linares、Joan Bosch

  DOI：10.1016/s0040-4039(00)99675-8

  日期：1989.1

  The first total synthesis of the indole alkaloid 19,20-dihydroakuammicine and detailed 1H- and 13C-NMR data of this alkaloid are reported.

  吲哚生物碱19,20-dihydroakuammicine的第一个全合成以及该生物碱的详细1 H-和13 C-NMR数据得到了报道。
• AMAT, MERCEDES;LINARES, ANA;BOSCH, JOAN, TETRAHEDRON LETT., 30,(1989) N7, C. 2293-2296
  作者：AMAT, MERCEDES、LINARES, ANA、BOSCH, JOAN

  DOI：——

  日期：——