硫双萍蓬定 | 30343-72-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹嗪类
• 中文名称: 硫双萍蓬定
• 英文名称: thiobinupharidine
• CAS: 30343-72-7
• 化学式: C₃₀H₄₂N₂O₂S
• 分子量: 494.742
• InChiKey: WBMOHCBEBDKSBI-JYZUVFRYSA-N

物化性质

• 熔点：
  129-130 °C
• 沸点：
  601.1±55.0 °C(predicted)
• 密度：
  1.20±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  35
• 可旋转键数：
  2
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  58.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  硫双萍蓬定 、 碘甲烷 以46%的产率得到
  参考文献：
  名称：

  WROBEL, JERZY T.;SCHOLL-ALEKSANDROWICZ, ANNA;CYBULSKI, JACEK;WOJTASIEWICZ+, COLLECT. CZECHOSL. CHEM. COMMUN., 54,(1989) N, C. 2229-2239

  摘要：

  DOI：
• 作为产物：
  描述：

  6-hydroxythionuphlutine B 在 sodium tetrahydroborate 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 24.5h， 生成 硫双萍蓬定
  参考文献：
  名称：

  Crude Drugs from Aquatic Plants. VI. On the Alkaloid Constituents of Chinese Nupharis Rhizoma, the Dried Rhizoma of Nuphar pumilum (TIMM.) DC. (Nymphaceae): Structures and Rearrangement Reaction of Thiohemiaminal Type Nuphar Alkaloids

  摘要：

  From Chinese Nupharis Rhizoma, the dried rhizoma of Nuphar pumilum (TIMM.) DC. (Nymphaceae), four thiohemiaminal type nuphar alkaloids with potent immuno-suppressive activity, 6-hydroxythiobinupharidine, 6,6'-dihydroxythiobinupharidine, 6-hydroxythionuphlutine B, 6'-hydroxythionuphlutine B, have been isolated together with nine inactive nuphar alkaloids. The configurations of the 6- and 6'-hydroxyl groups in those thiohemiaminal type nuphar alkaloids were confirmed on the basis of their 2D-NMR analysis. During the course of chemical elucidation of those thiaspirane type dimeric sesquiterpene alkaloids, new rearrangement reaction of the thiaspirane ring in thiohemiaminal type alkaloids with 6-hydroxyl group was found and the reaction pathway was discussed. By using this rearrangement reaction, 6-hydroxythionuphlutine B was chemically related with 6-hydroxythiobinupharidine, so that the absolute stereostructures of thionuphlutine B and its related compounds such as 6-hydroxythionuphlutine B, 6'-hydroxythionuphlutine B, and thionuphlutine B beta-sulfoxide, were characterized.

  DOI：

  10.3987/com-97-7878

文献信息

• Total Synthesis of Unsymmetrically Oxidized Nuphar Thioalkaloids via Copper-Catalyzed Thiolane Assembly
  作者：Jacob J. Lacharity、Jeremy Fournier、Ping Lu、Artur K. Mailyan、Aaron T. Herrmann、Armen Zakarian

  DOI：10.1021/jacs.7b07685

  日期：2017.9.27

  spirocyclic thietane. This strategy diverges both from the proposed biosynthesis1 and previous syntheses of this family of alkaloids,2,3 all of which employ dimerization of symmetric monomers to form the aforementioned thiaspirane. The coupling of unsymmetrical monomers allowed access to the unsymmetrically oxidized product 2b for the first time.

  描述了 (+)-6-羟基硫代联尿嘧啶 (1b) 和 (-)-6-羟基硫代联尿嘧啶 (2b) 的不对称全合成，这是一组从 Nuphar 属的黄睡莲中分离出来的含有二聚倍半萜的半缩醛胺。中心双螺环四氢噻吩环是通过锍叶立德的史蒂文斯重排形成的，锍叶立德是由铜卡宾与螺环硫杂环丁烷偶联而原位产生的。该策略与该生物碱家族所提出的生物合成1和之前的合成2,3都不同，所有这些都采用对称单体的二聚化来形成上述硫螺烷。不对称单体的偶联首次允许获得不对称氧化产物2b。
• Total Syntheses and Biological Evaluation of Both Enantiomers of Several Hydroxylated Dimeric Nuphar Alkaloids
  作者：Alexander Korotkov、Hui Li、Charles W. Chapman、Haoran Xue、John B. MacMillan、Alan Eastman、Jimmy Wu

  DOI：10.1002/anie.201503934

  日期：2015.9.1

  Herein, we describe the first total syntheses of five members of the dimeric nuphar alkaloids: (+)‐6,6′‐dihydroxythiobinupharidine (+)‐1 a, (+)‐6‐hydroxythiobinupharidine (+)‐1 b, (−)‐6,6′‐dihydroxythionuphlutine (−)‐2 a, (−)‐6,6′‐dihydroxyneothiobinupharidine (−)‐3 a, and (+)‐6,6′‐dihydroxyneothionuphlutine (+)‐4 a. The latter two have not been found in nature. We have also made each of their enantiomers

  在此，我们描述了二聚体Nuphar生物碱的五个成员的第一个总合成物：（+）-6,6'-二羟基硫代双up啶（+）- 1a，（+）-6-羟基硫代双up啶（+）- 1b，（- ）-6,6'- dihydroxythionuphlutine（ - ） - 2，（ - ） - 6,6'- dihydroxyneothiobinupharidine（ - ） - 3，和（+） - 6,6'- dihydroxyneothionuphlutine（+） - 4。后两者在自然界中尚未发现。我们还制作了它们的每个对映体（−）‐ 1 a – b，（+）‐ 2 a，（+）‐ 3 a和（−）‐ 4 a。这些合成的关键步骤是手性Lewis酸配合物使α-氨基腈（其相应的半胱氨酸的水解稳定替代物）二聚。对于那些在CD 3 OD中获得NMR光谱的情况，我们也将（+）- 1 a – 1 b的文献结构重新分配给了它们相应的CD
• The Hydride Reduction of Hemiaminals of Thiobinupharidine and the Structure of Thionupharoline
  作者：T. I. Martin、D. B. MacLean、J. T. Wróbel、A. Iwanow、W. Starzec

  DOI：10.1139/v74-394

  日期：1974.8.1

  Thionupharoline has been shown to be identical with 6-hydroxythiobinupharidine. The hydride reduction of hemiaminals of thiobinupharidine has been examined in ethanol solution. The steric course of reduction at C-6 is not nearly as selective as it has been reported to be in solution in methanol.

  Thionupharoline已被证明与6-羟基硫代比努法啶相同。已在乙醇溶液中检查了硫代比努法啶的半胺基的氢化还原。在C-6处还原的立体位阻效应并不像在甲醇溶液中报道的那样具有高选择性。
• Synthesis of (−)-Neothiobinupharidine
  作者：Daniel J. Jansen、Ryan A. Shenvi

  DOI：10.1021/ja310778t

  日期：2013.1.30

  An eight step, asymmetric synthesis of a dimeric thiaspirane nuphar alkaloid from 3-methyl-2-cyclopentenone is reported. The brevity of the route relies on a useful procedure for tandem reductive allylation of cyclopentenones, as well as the minimization of redox manipulations and other functional group interconversions. The distribution of products that arise from spontaneous dimerization points to a more complex biosynthesis.
• WROBEL, JERZY T.;SCHOLL-ALEKSANDROWICZ, ANNA;CYBULSKI, JACEK;WOJTASIEWICZ+, COLLECT. CZECHOSL. CHEM. COMMUN., 54,(1989) N, C. 2229-2239
  作者：WROBEL, JERZY T.、SCHOLL-ALEKSANDROWICZ, ANNA、CYBULSKI, JACEK、WOJTASIEWICZ+

  DOI：——

  日期：——