6-hydroxythionuphlutine B | 183072-79-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹嗪类
• 英文名称: 6-hydroxythionuphlutine B
• 英文别名: (-)-6-hydroxythionuphlutine
• CAS: 183072-79-9
• 化学式: C₃₀H₄₂N₂O₃S
• 分子量: 510.741
• InChiKey: GAKRXIIHJWAJNM-YMIHBEBRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  36
• 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：
  78.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  (-)-(3R)-methyl-4-penten-1-ol 在 咪唑 、 sodium tetrahydroborate 、 cadmium-lead couple 、 Wilkinson's catalyst 、 四(三苯基膦)钯 、 正丁基锂 、 Hoveyda-Grubbs catalyst second generation 、 bis(1,1,1-trifluoroacetylacetonato)copper(II) 、 sodiumsulfide nonahydrate 、 叠氮磷酸二苯酯 、 苯硅烷 、 ammonium acetate 、 氢气 、 碘 、 四丁基碘化铵 、 二异丁基氢化铝 、 溶剂黄146 、 二异丙胺 、 N,N-二异丙基乙胺 、 三苯基膦 、 N¹,N³-bis((R)-1-phenyl-2-(piperidin-1-yl)ethyl)propane-1,3-diamine 、 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 苯 为溶剂， -89.0~110.0 ℃ 、2.07 MPa 条件下， 反应 151.42h， 生成 6-hydroxythionuphlutine B
  参考文献：
  名称：

  铜催化硫杂环戊烷组装全合成不对称氧化的母花硫代生物碱

  摘要：

  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。

  DOI：

  10.1021/jacs.7b07685

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。
• 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
  作者：Masayuki Yoshikawa、Toshiyuki Murakami、Shuji Wakao、Atsushi Ishikado、Nobutoshi Murakami、Johji Yamahara、Hisashi Matsuda

  DOI：10.3987/com-97-7878

  日期：——

  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.