28-O-pivaloylbetulin | 1159113-91-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 28-O-pivaloylbetulin
• 英文别名: ((1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13aR,13bR)-9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-3aH-cyclopenta[a]chrysen-3a-yl)methyl pivalate；[(1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13aR,13bR)-9-hydroxy-1-isopropenyl-5a,5b,8,8,11a-pentamethyl-1,2,3,4,5,6,7,7a,9,10,11,11b,12,13,13a,13b-hexadecahydrocyclopenta[a]chrysen-3a-yl]methyl 2,2-dimethylpropanoate；[(1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13aR,13bR)-9-hydroxy-5a,5b,8,8,11a-pentamethyl-1-prop-1-en-2-yl-1,2,3,4,5,6,7,7a,9,10,11,11b,12,13,13a,13b-hexadecahydrocyclopenta[a]chrysen-3a-yl]methyl 2,2-dimethylpropanoate
• CAS: 1159113-91-3
• 化学式: C₃₅H₅₈O₃
• 分子量: 526.844
• InChiKey: IDAQBLCLBFLXBU-FKYYSFFJSA-N

物化性质

• 沸点：
  563.1±23.0 °C(predicted)
• 密度：
  1.006±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.3
• 重原子数：
  38
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  28-O-pivaloylbetulin 在 tetrabutylphosphonium dimethyl phosphate 、 palladium 10% on activated carbon 、 2,4,6-Triisopropylthiophenol 、 Ir[dF(CF₃)ppy]₂(5,5'-dCF₃bpy)PF₆ 、 氢气 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 96.0h， 生成 ((3S,4S,5R,8R,9S,10R,13S,14R,15S)-3,15-diisopropyl-4,9,10-trimethyl-4-(3-oxopropyl)hexadecahydro-13H-cyclopenta[a]phenanthren-13-yl)methyl pivalate
  参考文献：
  名称：

  用于光驱动、失衡异构化的氧化还原策略及其在催化 C-C 键裂解反应中的应用

  摘要：

  我们报告了光驱动的环状脂肪醇异构化为线性羰基化合物的通用协议。这些反应通过醇 OH 键的质子耦合电子转移活化进行，随后生成的烷氧基自由基中间体的 CC β 断裂。在许多情况下，这些氧化还原中性异构化与显着的能量梯度相反，产生的产品热力学稳定性低于起始材料。提出了一种机制来合理化这种不平衡行为，该机制可以作为设计由激发态氧化还原事件驱动的其他逆热力学转换的模型。

  DOI：

  10.1021/jacs.8b12552
• 作为产物：
  描述：

  白桦脂醇 、 三甲基乙酰氯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 0.08h， 以54%的产率得到28-O-pivaloylbetulin
  参考文献：
  名称：

  Isolation, Structural Modification, and HIV Inhibition of Pentacyclic Lupane-Type Triterpenoids from Cassine xylocarpa and Maytenus cuzcoina

  摘要：

  As a part of our investigation into new anti-HIV agents, we report herein the isolation, structure elucidation, and biological activity of six new (1-6) and 20 known (7-26) pentacyclic lupane-type triterpenoids from the stem of Cassine xylocarpa and root bark of Maytenus cuzcoina. Their stereo-structures were elucidated on the basis of spectroscopic and spectrometric methods, including ID and 2D NMR techniques. To gain a more complete understanding of the structural requirements for anti-HIV activity, derivatives 27-48 were prepared by chemical modification of the main secondary metabolites. Sixteen compounds from this series displayed inhibitory effects of human immunodeficiency virus type 1 replication with IC50 values in the micromolar range, highlighting compounds 12, 38, and 42 (IC50 4.08, 4.18, and 1.70 mu M, respectively) as the most promising anti-HIV agents.

  DOI：

  10.1021/np501025r

文献信息

• Synthesis, cytotoxicity, and haemolytic activity of chacotrioside lupane-type neosaponins and their germanicane-type rearrangement products
  作者：Charles Gauthier、Jean Legault、Marianne Piochon、Serge Lavoie、Samuel Tremblay、André Pichette

  DOI：10.1016/j.bmcl.2009.02.076

  日期：2009.4

  The concise synthesis, via a stepwise glycosylation approach, of lupeol, betulin and betulinic acid O-glycosides bearing a chacotriosyl moiety at the C-3 position is described. All neosaponins as well as their rearrangement products of the germanicane-type were evaluated in vitro for their anticancer and haemolytic activities. Although betulinic acid and betulin 3 beta-O-chacotriosides were neither cytotoxic nor haemolytic, their rearrangement products allobetulin and 28-oxoallobetulin 3 beta-O-chacotriosides (9 and 10) exhibited a cytotoxicity pro. le up to fourfold superior to betulinic acid against human breast (MCF7) and prostate (PC-3) adenocarcinomas cell lines (IC(50) = 10-18 mu M). One important result was that only chacotriosides featuring non-polar functions at the C-28 position (6, 9 and 10) exerted a haemolytic activity against red blood cells. (c) 2009 Elsevier Ltd. All rights reserved.
• A Redox Strategy for Light-Driven, Out-of-Equilibrium Isomerizations and Application to Catalytic C–C Bond Cleavage Reactions
  作者：Eisuke Ota、Huaiju Wang、Nils Lennart Frye、Robert R. Knowles

  DOI：10.1021/jacs.8b12552

  日期：2019.1.30

  We report a general protocol for the light-driven isomerization of cyclic aliphatic alcohols to linear carbonyl compounds. These reactions proceed via proton-coupled electron-transfer activation of alcohol O-H bonds followed by subsequent C-C β-scission of the resulting alkoxy radical intermediates. In many cases, these redox-neutral isomerizations proceed in opposition to a significant energetic gradient

  我们报告了光驱动的环状脂肪醇异构化为线性羰基化合物的通用协议。这些反应通过醇 OH 键的质子耦合电子转移活化进行，随后生成的烷氧基自由基中间体的 CC β 断裂。在许多情况下，这些氧化还原中性异构化与显着的能量梯度相反，产生的产品热力学稳定性低于起始材料。提出了一种机制来合理化这种不平衡行为，该机制可以作为设计由激发态氧化还原事件驱动的其他逆热力学转换的模型。
• Isolation, Structural Modification, and HIV Inhibition of Pentacyclic Lupane-Type Triterpenoids from <i>Cassine xylocarpa</i> and <i>Maytenus cuzcoina</i>
  作者：Oliver Callies、Luis M. Bedoya、Manuela Beltrán、Alejandro Muñoz、Patricia Obregón Calderón、Alex A. Osorio、Ignacio A. Jiménez、José Alcamí、Isabel L. Bazzocchi

  DOI：10.1021/np501025r

  日期：2015.5.22

  As a part of our investigation into new anti-HIV agents, we report herein the isolation, structure elucidation, and biological activity of six new (1-6) and 20 known (7-26) pentacyclic lupane-type triterpenoids from the stem of Cassine xylocarpa and root bark of Maytenus cuzcoina. Their stereo-structures were elucidated on the basis of spectroscopic and spectrometric methods, including ID and 2D NMR techniques. To gain a more complete understanding of the structural requirements for anti-HIV activity, derivatives 27-48 were prepared by chemical modification of the main secondary metabolites. Sixteen compounds from this series displayed inhibitory effects of human immunodeficiency virus type 1 replication with IC50 values in the micromolar range, highlighting compounds 12, 38, and 42 (IC50 4.08, 4.18, and 1.70 mu M, respectively) as the most promising anti-HIV agents.