2,3,22,23-tetra-O-acetyl-6a-carbabrassinolide | 220809-23-4

• 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: 2,3,22,23-tetra-O-acetyl-6a-carbabrassinolide
• 英文别名: [(1S,2R,4R,5S,7S,11S,12S,15R,16S)-4-acetyloxy-15-[(2S,3R,4R,5S)-3,4-diacetyloxy-5,6-dimethylheptan-2-yl]-2,16-dimethyl-8-oxo-5-tetracyclo[9.7.0.02,7.012,16]octadecanyl] acetate
• CAS: 220809-23-4
• 化学式: C₃₇H₅₈O₉
• 分子量: 646.862
• InChiKey: VRBCTSCCWCVNQX-DVLSSGJOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  46
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  122
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2,3,22,23-tetra-O-acetyl-6a-carbabrassinolide 在 氢氧化钾 、 三氟化硼乙醚 作用下， 以 甲醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 10.0h， 生成 6a-carba-B-homobrassinolide
  参考文献：
  名称：

  6a-氨基甲磺酰基内酯及其相关化合物的制备，构象分析和生物学评价

  摘要：

  为了探测油菜素内酯（BR）受体的配体识别位点，使用B环修饰的油菜素内酯（BLs），即6a-carbaBL（3），6a-carba-B-homoBL（4），C-5差向异构体化合物3和4（分别为6和7）以及6-脱氧6a-氧6a-carbaBL（8）是由蓖麻固酮（2）通过与三甲基甲硅烷基重氮甲烷和三氟化硼醚化物同源制备的。使用大米薄层倾斜度（RLI）测试对这些化合物进行生物学评估，得出以下效力顺序（活性百分比）：BL（1）（100％）> 2（13％）> 3（0.3％）≫4，6，7，8（0％）。使用BR缺陷型突变体拟南芥属det2的下胚轴长度的挽救测试，相应顺序为：1（100％）> 8（44％）> 2（28％）> 3（4％）> 6（0.5％） > 4（0.1％）和7（抑制）。两个测定系统中8的明显不同的活性提供了明显的实验证据，证明参与RLI和拟南芥下胚轴伸长的BR受体至少在B环区域以不同的结构方式识别BR分子。

  DOI：

  10.1016/s0040-4020(02)01247-4
• 作为产物：
  描述：

  重氮甲烷 、 2,3,22,23-tetra-O-acetylcastasterone 在 三氟化硼乙醚 作用下， 以 乙醚 为溶剂， 反应 24.0h， 以33%的产率得到2,3,22,23-tetra-O-acetyl-6a-carbabrassinolide
  参考文献：
  名称：

  Structure–activity studies of brassinolide B-ring analogues

  摘要：

  Six new analogues of brassinolide were prepared in order to investigate their structure-activity relationship: 7-azabrassinolide, 7-thiabrassinolide, 6-deoxybrassinolide, B-homocastasterone, 6-methylidene-castasterone and 6-methylidene-B-homocastasterone. These compounds were subjected to the rice leaf lamina inclination assay, in comparison with brassinolide and 24-epibrassinolide and/or castasterone to test for brassinosteroid activity. The activity of 7-azabrassinolide, 7-thiabrassinolide and 6-deoxybrassinolide was comparable to that of 24-epibrassinolide, but lower than that of brassinolide. B-Homocastasterone was less active than either brassinolide or castasterone. The B-ring carbocycles 6-methylidene-castasterone and 6-methylidene-B-homocastasterone were essentially inactive. These results indicate that neither the oxygen atom at the 7-position of brassinolide, nor its carbonyl group, is essential for activity. However, the complete absence of a polar functional group from the B-ring, as in 6-methylidenecastasterone and 6-methylidene-B-homocastasterone, results in a total loss of bioactivity. This inactivity persists even in the presence of an exocyclic methylidene group that flattens the B-ring to resemble that of brassinolide or castasterone by virtue of the sp(2)-hybridized carbon atom at C-6. Finally, the bioactivity of several, but not all, of the brassinosteroids, was significantly and synergistically increased by the simultaneous application of the auxin, indole-3-acetic acid. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0031-9422(98)00367-7

文献信息

• Synthesis and biological activity of 6a-carbabrassinolide: B-ring homologation of 6-oxo-steroid to 6-oxo-7a-homosteroid with trimethylsilyldiazomethane-boron trifluoride etherate
  作者：Hideharu Seto、Shozo Fujioka、Hiroyuki Koshino、Hideki Hayasaka、Takeshi Shimizu、Shigeo Yoshida、Tsuyoshi Watanabe

  DOI：10.1016/s0040-4039(99)00186-0

  日期：1999.3

  From castasterone (10), 6a-carbabrassinolide (2) was synthesized via a highly regioselective B-ring homologation with trimethylsilyldiazomethane and boron trifluoride etherate. A preliminary experiment using a simple 6-oxo-steroid (3) revealed that the actual products of this homologation reaction were α-trimethylsilyl ketones (4) and (5), which were converted to 6 (79%) and 7 (7.2%) by acid treatment

  通过三区域甲硅烷基重氮甲烷和三氟化硼醚化物的高度区域选择性B环同系物，从蓖麻甾酮（10）合成了6a-氨基甲酸酯（2）。使用简单的6-氧-甾族化合物（3）进行的初步实验表明，该同源反应的实际产物是α-三甲基甲硅烷基酮（4）和（5），它们分别转化为6（79％）和7（7.2％） ）经酸处理。的生物活性2在水稻叶片倾斜测试是CA。相比1，这表明在该图6a-氧1 是这项活动的重要但非必要因素。