brassicasterol

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: brassicasterol
• 英文别名: Brabetaicasterol；(3S,9S,10R,13R,14S,17R)-17-[(E,2R,5R)-5,6-dimethylhept-3-en-2-yl]-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-ol
• 化学式: C₂₈H₄₆O
• 分子量: 398.673
• InChiKey: OILXMJHPFNGGTO-KDISEMKTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  一氧化碳 、 1-叠氮基-4-甲氧基苯 、 brassicasterol 在 三乙胺 、 palladium dichloride 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 70.0 ℃ 、101.33 kPa 条件下， 反应 24.0h， 以57%的产率得到(3S,9S,10R,13R,14R,17R)-17-((2R,5R,E)-5,6-dimethylhept-3-en-2-yl)-10,13-dimethyl-2,3,4,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl4-methoxyphenylcarbamate
  参考文献：
  名称：

  PdCl2 catalyzed efficient assembly of organic azides, CO, and alcohols under mild conditions: a direct approach to synthesize carbamates

  摘要：

  开发了一种通过异氰酸酯的生成及原位应用，利用简单易得的PdCl2催化合成氨基甲酸酯的方法。该化学合成法提供了一种高效实用的途径，可以从简单的有机叠氮化合物、CO气氛和醇合成氨基甲酸酯。该转化的广泛适用性、温和中性条件以及仅产生氮气作为副产物，使其非常有用。此外，通过该方法还实现了对生物活性分子的简单修饰和构建大环化合物。

  DOI：

  10.1039/c4cc00538d
• 作为产物：
  描述：

  麦角固醇 在 lithium 、 乙胺 作用下， 生成 brassicasterol
  参考文献：
  名称：

  Biosynthetic studies of marine lipids. 33. Biosynthesis of dinosterol, peridinosterol and gorgosterol: unusual patterns of bioalkylation in dinoflagellate sterols

  摘要：

  The biosynthesis of the 23-methylated dinoflagellate sterols gorgosterol (1-N), dinosterol (2-K), and peridinosterol (3-K) was demonstrated experimentally using cell-free extracts of the dinoflagellates Cryptothecodinium cohnii, Peridinium foliaceum, and the cultured zooxanthella symbiont of Cassiopea xamachana. In assays of sterol methyltransferases using [H-3]-S-adenosylmethionine, radiochemical conversions were demonstrated by reverse phase HPLC of the DELTA-24 sterol side chain (5) to the 24-methylene side chain (4); of the sequence 24(R)-4-alpha-methylergost-22-enol (9-K) to dinosterol (2-K) to 4-alpha-methylgorgostanol (1-K); and, in P. foliaceum, of 24-(R)-4-alpha-methylergost-22-enol (9-K) to peridinosterol (3-K). Methylation of the 24(R)-methyl DELTA-22 side chain (9) in P. foliaceum is believed to involve more than one SAM-sterol methyltransferase based on changes in the ratios of the products (2 and 3) with changes in the conditions of the assay. Furthermore, deuterium substitution of the sterol substrate (9-K) at C-23 did not significantly alter the product ratio. A hypothesis is put forward that the attenuation of gorgosterol (1-N) production in aposymbiotic zooxanthellae is linked to an increase in dimethylpropiothetin biosynthesis via a decrease in S-adenosylmethionine concentration.

  DOI：

  10.1021/jo00007a021

文献信息

• PdCl2 catalyzed efficient assembly of organic azides, CO, and alcohols under mild conditions: a direct approach to synthesize carbamates
  作者：Long Ren、Ning Jiao

  DOI：10.1039/c4cc00538d

  日期：——

  A simple and readily available PdCl2 catalyzed carbamate synthesis method via isocyanate generation and application in situ has been developed. This chemistry provides an efficient and practical approach to synthesize carbamates from simple organic azides, CO atmosphere and alcohols. The broad scope, mild and neutral conditions, and only N2 as the byproduct make this transformation very useful. Moreover, simple examples of modification of bioactive molecules and construction of macrocycles were achieved through this protocol.

  开发了一种通过异氰酸酯的生成及原位应用，利用简单易得的PdCl2催化合成氨基甲酸酯的方法。该化学合成法提供了一种高效实用的途径，可以从简单的有机叠氮化合物、CO气氛和醇合成氨基甲酸酯。该转化的广泛适用性、温和中性条件以及仅产生氮气作为副产物，使其非常有用。此外，通过该方法还实现了对生物活性分子的简单修饰和构建大环化合物。
• Biosynthetic studies of marine lipids. 33. Biosynthesis of dinosterol, peridinosterol and gorgosterol: unusual patterns of bioalkylation in dinoflagellate sterols
  作者：Jose Luis Giner、Carl Djerassi

  DOI：10.1021/jo00007a021

  日期：1991.3

  The biosynthesis of the 23-methylated dinoflagellate sterols gorgosterol (1-N), dinosterol (2-K), and peridinosterol (3-K) was demonstrated experimentally using cell-free extracts of the dinoflagellates Cryptothecodinium cohnii, Peridinium foliaceum, and the cultured zooxanthella symbiont of Cassiopea xamachana. In assays of sterol methyltransferases using [H-3]-S-adenosylmethionine, radiochemical conversions were demonstrated by reverse phase HPLC of the DELTA-24 sterol side chain (5) to the 24-methylene side chain (4); of the sequence 24(R)-4-alpha-methylergost-22-enol (9-K) to dinosterol (2-K) to 4-alpha-methylgorgostanol (1-K); and, in P. foliaceum, of 24-(R)-4-alpha-methylergost-22-enol (9-K) to peridinosterol (3-K). Methylation of the 24(R)-methyl DELTA-22 side chain (9) in P. foliaceum is believed to involve more than one SAM-sterol methyltransferase based on changes in the ratios of the products (2 and 3) with changes in the conditions of the assay. Furthermore, deuterium substitution of the sterol substrate (9-K) at C-23 did not significantly alter the product ratio. A hypothesis is put forward that the attenuation of gorgosterol (1-N) production in aposymbiotic zooxanthellae is linked to an increase in dimethylpropiothetin biosynthesis via a decrease in S-adenosylmethionine concentration.