(-)-N_b-methylraumacline | 132943-65-8

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 大灵碱生物碱
• 英文名称: (-)-N_b-methylraumacline
• 英文别名: N_β-methylraumacline；(1S,12S,13S,14R,17S,18S)-17-ethyl-3,20-dimethyl-15-oxa-3,20-diazapentacyclo[10.7.1.02,10.04,9.013,18]icosa-2(10),4,6,8-tetraen-14-ol
• CAS: 132943-65-8
• 化学式: C₂₁H₂₈N₂O₂
• 分子量: 340.466
• InChiKey: RTPWCEXWSHQRPA-SZCDOQLDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  25
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  37.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (-)-N_b-benzylraumacline 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 反应 48.0h， 以85%的产率得到(-)-N_b-methylraumacline
  参考文献：
  名称：

  General approach for the synthesis of ajmaline-related alkaloids. Enantiospecific total synthesis of (-)-suaveoline, (-)-raumacline, and (-)-Nb-methylraumacline

  摘要：

  本研究成功地通过不对称方式利用D-(+)-色氨酸合成了从Rauwolfia serpentina Benth.植物细胞培养物中分离出的(-)-Raumacline(3)和(-)-Nb-甲基raumacline(4)。此外，(-)-Suaveoline(1)也通过该方法成功制备。在吲哚类生物碱的合成过程中，采用了一种立体特异的Pictet-Spengler/Dieckmann协议来制备关键中间体(-)-N(b)-苄基四环酮(12)。随后，通过阴离子氧-Cope重排，将酮12转化为C-15功能化系统16；另外，通过将Grignard试剂与从(-)-12生成的α,β-不饱和醛(-)-8进行1,4-加成，也获得了16。将16分别转化为(-)-N(b)-苄基suaveoline(23)或(-)-N(b)-苄基raumacline(28)的过程得到了详细描述。通过在乙醇中使用乙醇的催化脱苄基反应，分别以优异的产率得到了相应的生物碱(-)-1和(-)-3。与已发布的报告不同，(-)-Suaveoline的光学旋转被发现为[α]D25 = -9.3度（c = 0.30，CHCl3），而不是先前报告的0度。将23或28分别与过量的Pd/C和氢气在甲醇中处理，分别以优异的产率得到了(-)-N(b)-甲基suaveoline和(-)-N(b)-甲基raumacline。

  DOI：

  10.1021/jo00055a019

文献信息

• Biotransformation of ajmaline in plant cell cultures of rauwolfia serpentina benth.: The new indole alkaloids raumacline and N(b)-methylraumacline.
  作者：Leo Polz、Joachim Stöckigt、Hiromitsu Takayama、Naoki Uchida、Norio Aimi、Shin-ichiro Sakai

  DOI：10.1016/s0040-4039(00)97149-1

  日期：1990.1

  Two novel indole alkaloids, raumacline (2) and N(b)-methylraumacline (3), were isolated from plant cell cultures of Rauwolfia serpentina Benth. after feeding experiments with the Rauwolfia alkaloid ajmaline (1). The structures of the new alkaloids were elucidated by spectroscopic methods and chemical synthesis from ajmaline (1).

  从Rauwolfia serpentina Benth的植物细胞培养物中分离出两种新颖的吲哚生物碱，raumacline（2）和N （b） -methylraumacline（3）。后与进给实验萝芙木生物碱阿义马林（1）。新光谱生物碱的结构通过光谱学方法和阿玛琳的化学合成得以阐明（1）。
• Enzymatic biosynthesis of raumacline
  作者：Peter Obitz、Susanne Endreß、Joachim Stöckigt

  DOI：10.1016/0031-9422(95)00503-y

  日期：1995.11

  The indole alkaloid, raumacline, is biosynthesized from ajmaline, when the latter was fed to cell suspensions of Rauwolfia serpentina. Formation in catalysed by two enzymes, a cell wall-bound peroxidase following by a NADPH(2)-dependent reductase. The first enzyme cleaves ajmaline oxidatively leading to a C-21 epimeric mixture of 21-hydroxyraumacline, a novel alkaloid, which, in turn, is reduced under formation of raumacline. The peroxidase reaction is not specific for Rauwolfia cells whereas the reductase is present exclusively in Rauwolfia cell suspensions. The reductase has been purified to homogeneity. The enzyme is highly substrate specific, only accepting 21-hydroxyraumacline and perakine, the latter leading to raucaffrinoline by reduction.
• Enantiospecific total synthesis of the ajmaline related alkaloids (-)-suaveoline, (-)-raumacline, and (-)-Nb-methylraumacline
  作者：Xiaoyong Fu、James M. Cook

  DOI：10.1021/ja00043a043

  日期：1992.8
• POLZ, LEO;STOCKIGT, JOACHIM;TAKAYAMA, HIROMITSU;UCHIDA, NAOKI;AIMI, NORIO+, TETRAHEDRON LETT., 31,(1990) N6, C. 6693-6696
  作者：POLZ, LEO、STOCKIGT, JOACHIM、TAKAYAMA, HIROMITSU、UCHIDA, NAOKI、AIMI, NORIO+

  DOI：——

  日期：——
• General approach for the synthesis of ajmaline-related alkaloids. Enantiospecific total synthesis of (-)-suaveoline, (-)-raumacline, and (-)-Nb-methylraumacline
  作者：Xiaoyong Fu、James M. Cook

  DOI：10.1021/jo00055a019

  日期：1993.1

  (-)-Raumacline (3) and (-)-Nb-methylraumacline (4), isolated from plant cell cultures of Rauwolfia serpentina Benth., have been synthesized from D-(+)-tryptophan in enantiospecific fashion. In addition, (-)-suaveoline (1) has also been prepared via this strategy. The synthesis of these indole alkaloids employed a stereospecific Pictet-Spengler/Dieckmann protocol to prepare the key intermediate, (-)-N(b)-benzyltetracyclic ketone 12. This ketone 12 was converted into the C-15 functionalized system 16 via an anionic oxy-Cope rearrangement; 16 had also been obtained by 1,4-addition of a Grignard reagent to the alpha,beta-unsaturated aldehyde (-)-8 generated from (-)-12. Conversion of 16 into either (-)-N(b)-benzylsuaveoline (23) or (-)-N(b)-benzylraumacline (28), respectively, is described. Catalytic debenzylation of the hydrochloride salts of 23 and 28 in ethanol provided the corresponding alkaloids (-)-1 and (-)-3 in excellent yield. In contrast to the published reports, the optical rotation of (-)-suaveoline (>98% ee) was found to be [alpha]25D = -9.3-degrees (c = 0.30, CHCl3) rather than 0-degrees as previously reported. Treatment of 23 or 28 (individually) with excess Pd/C and hydrogen in methanol yielded (-)-N(b)-methylsuaveoline and (-)-N(b)-methylraumacline in excellent yield, respectively.

  本研究成功地通过不对称方式利用D-(+)-色氨酸合成了从Rauwolfia serpentina Benth.植物细胞培养物中分离出的(-)-Raumacline(3)和(-)-Nb-甲基raumacline(4)。此外，(-)-Suaveoline(1)也通过该方法成功制备。在吲哚类生物碱的合成过程中，采用了一种立体特异的Pictet-Spengler/Dieckmann协议来制备关键中间体(-)-N(b)-苄基四环酮(12)。随后，通过阴离子氧-Cope重排，将酮12转化为C-15功能化系统16；另外，通过将Grignard试剂与从(-)-12生成的α,β-不饱和醛(-)-8进行1,4-加成，也获得了16。将16分别转化为(-)-N(b)-苄基suaveoline(23)或(-)-N(b)-苄基raumacline(28)的过程得到了详细描述。通过在乙醇中使用乙醇的催化脱苄基反应，分别以优异的产率得到了相应的生物碱(-)-1和(-)-3。与已发布的报告不同，(-)-Suaveoline的光学旋转被发现为[α]D25 = -9.3度（c = 0.30，CHCl3），而不是先前报告的0度。将23或28分别与过量的Pd/C和氢气在甲醇中处理，分别以优异的产率得到了(-)-N(b)-甲基suaveoline和(-)-N(b)-甲基raumacline。