5α-cholestan-3β-yl allyl ether | 108741-19-1

• 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: 5α-cholestan-3β-yl allyl ether
• 英文别名: allyl 5α-cholestan-3β-yl ether；allyl 3β-cholestanyl ether；(3S,5S,8R,9S,10S,13R,14S,17R)-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-3-prop-2-enoxy-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthrene
• CAS: 108741-19-1
• 化学式: C₃₀H₅₂O
• 分子量: 428.742
• InChiKey: TVUALZLMWGQULY-QYHGRWQDSA-N

物化性质

• 沸点：
  491.0±14.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.5
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5α-cholestan-3β-yl allyl ether 在 caesium carbonate 、 1-(过氧化叔丁基)-1,2-苯碘酰-3(H)-酮 作用下， 以 环己烷 为溶剂， 反应 110.0h， 以62%的产率得到[(3S,5S,8R,9S,10S,13R,14S,17R)-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl] prop-2-enoate
  参考文献：
  名称：

  高价（叔丁基过氧）碘在室温下在溶液中生成以碘为中心的自由基：苄基和烯丙基醚的氧化和脱保护，以及生成 α-氧碳自由基的证据

  摘要：

  1-(tert-Butylperoxy)-1,2-benziodoxol-3(1H)-one (1a) 在室温下，在苯或环己烷中，在碱金属碳酸盐存在下，将苄基和烯丙基醚氧化成酯。由于该反应与其他保护基团（例如 MOM、THP 和 TBDMS 醚以及乙酰氧基）相容，并且由于酯在碱性条件下容易水解，因此这种新方法为通常的还原性脱保护提供了一种方便有效的替代方法。与 1a 的氧化很容易发生，C-H 键被焓效应（苄基、烯丙基和炔丙基 C-H 键）和/或极性效应（α-氧 C-H 键）激活，生成 α-氧碳中心自由基，可以通过硝酰基自由基捕获来检测。

  DOI：

  10.1021/ja9610287
• 作为产物：
  描述：

  3β-胆甾烷醇 、 3-溴丙烯 在 sodium hydride 、 potassium carbonate 、 sodium iodide 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 生成 5α-cholestan-3β-yl allyl ether
  参考文献：
  名称：

  Phosphoramidate derivatives of hydroxysteroids as inhibitors of prostate-specific membrane antigen

  摘要：

  Prostate-specific membrane antigen (PSMA) is a membrane-bound cell surface peptidase which is over-expressed in prostate cancer cells. The enzymatic activities of PSMA are understood but the role of the enzyme in prostate cancer remains conjectural. We previously confirmed the existence of a hydrophobic binding site remote from the enzyme's catalytic center. To explore the specificity and accommodation of this binding site, we prepared a series of six glutamate-containing phosphoramidate derivatives of various hydroxysteroids (1a-1f). The inhibitory potencies of the individual compounds of the series were comparable to a simple phenylalkyl analog (8), and in all cases IC50 values were sub-micromolar. Molecular docking was used to develop a binding model for these inhibitors and to understand their relative inhibitory potencies against PSMA. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2007.10.096

文献信息

• AlCl3-N,N-dimethylaniline: A new benzyl and allyl ether cleavage reagent.
  作者：Takahiko Akiyama、Hajimu Hirofuji、Shoichiro Ozaki

  DOI：10.1016/s0040-4039(00)79656-0

  日期：1991.3

  Benzyl and allyl ethers have been cleaved readily on treatment with AlCl3 and N,N-dimethylaniline to give parent alcohols in high yields. Comparisons of N,N-dimethylaniline and anisole are also described.

  在用AlCl 3和N，N-二甲基苯胺处理后，苄基和烯丙基醚很容易裂解，从而以高收率得到母体醇。还描述了N，N-二甲基苯胺和苯甲醚的比较。
• AlCl₃–<i>N</i>,<i>N</i>-Dimethylaniline: A Novel Benzyl and Allyl Ether Cleavage Reagent
  作者：Takahiko Akiyama、Hajimu Hirofuji、Shoichiro Ozaki

  DOI：10.1246/bcsj.65.1932

  日期：1992.7

  A combination system of AlCl3–N,N-dimethylaniline was found to cleave benzyl ethers readily to give parent alcohols in excellent yields. The system also cleaved allyl as well as methyl ethers. Numerous functional groups such as benzoyloxy, phenylthio, and olefinic double bond were not affected. Comparisons of AlCl3–N,N-dimethylaniline and AlCl3–anisole were described.

  发现 AlCl3–N,N-二甲基苯胺的组合系统很容易裂解苄基醚，以优异的产率得到母体醇。该系统还裂解烯丙基以及甲基醚。许多官能团如苯甲酰氧基、苯硫基和烯属双键不受影响。描述了 AlCl3-N,N-二甲基苯胺和 AlCl3-苯甲醚的比较。
• Amine-Induced Selective C–C Bond Cleavage of 2,2,2-Trifluoroethyl Carbonyls for the Synthesis of Ureas and Amides
  作者：Kuantao Mao、Leiyang Lv、Zhiping Li

  DOI：10.1021/acs.joc.3c00979

  日期：2023.7.21

  An efficient and selective transformation of 2,2,2-trifluoroethyl carbonyls into ureas/amides with amines is reported. This protocol allows the selective cleavage of the C–C bond of 2,2,2-trifluoroethyl carbonyls under transition metal-free and oxidant-free conditions, which is in contrast to the analogous C–F or C–CF3 bond functionalization. This reaction reveals the unexplored reactivity of 2,2,2-trifluoroethyl

  据报道，2,2,2-三氟乙基羰基与胺有效且选择性地转化为脲/酰胺。该方案允许在无过渡金属和无氧化剂的条件下选择性裂解 2,2,2-三氟乙基羰基的 C-C 键，这与类似的 C-F 或 C-CF 3 键功能化相反。该反应揭示了 2,2,2-三氟乙基羰基的未开发反应性，并表现出广泛的底物范围和良好的官能团耐受性。
• Photosensitized O ₂ enables intermolecular alkene cyclopropanation by active methylene compounds
  作者：Dhruba P. Poudel、Amrit Pokhrel、Raj Kumar Tak、Majji Shankar、Ramesh Giri

  DOI：10.1126/science.adg3209

  日期：2023.8.4

  Cyclopropanes are key features in many preclinical, clinical, and commercial drugs, as well as natural products. The most prolific technique for their synthesis is the metal-catalyzed reaction of an alkene with a diazoalkane, a highly energetic reagent requiring stringent safety precautions. Discovery of alternative innocuous reagents remains an ongoing challenge. Herein, we report a simple photoredox-catalyzed

  环丙烷是许多临床前、临床和商业药物以及天然产物的关键特征。最丰富的合成技术是烯烃与重氮烷的金属催化反应，重氮烷是一种高能试剂，需要严格的安全预防措施。发现替代的无害试剂仍然是一个持续的挑战。在此，我们报道了未活化烯烃与活性亚甲基化合物的简单光氧化还原催化分子间环丙烷化反应。反应在中性溶剂中在空气或分子氧（O 2 ）与由蓝色发光二极管光激发的光氧化还原催化剂和碘助催化剂（以分子碘形式添加或由烷基碘原位生成）。机理研究表明光敏 O 2在活性亚甲基化合物与烯烃的加成和环闭合过程中碳中心自由基的生成中起着至关重要的作用。
• Examples of amphitropic polymers: monolayer film, Langmuir–Blodgett film and liquid-crystalline properties of some polymeric amphiphiles containing cholestanol moieties and those of some closely related non-polymeric amphiphiles
  作者：Ziad Ali-Adib、Andrea Bomben、Frank Davis、Philip Hodge、Pietro Tundo、Ludovico Valli

  DOI：10.1039/jm9960600015

  日期：——

  A range of alternating copolymers were prepared by free-radical-initiated copolymerizations of maleic anhydride with a series of alpha-alkenes containing cholestanyl moieties. Derivatives of these copolymers were prepared by reacting the anhydride residues with methanol, water, dimethylamine and/or morpholine. A related series of non-polymeric amphiphiles containing steroid moieties was also prepared. Isotherms were measured for monolayers of the various polymers and the various non-polymeric amphiphiles on water and, where possible, Langmuir-Blodgett (LB) multilayers were prepared. The majority of the materials gave good isotherms (relatively steep with collapse pressures >40 mN m(-1)) indicating that the monolayers were ordered and, as determined by the detection of Bragg peaks by X-ray diffraction, Y-type LB films with regular layer structures. Appropriate materials were also examined, by optical microscopy and differential scanning calorimetry (DSC), for possible liquid-crystalline properties. Four polymers and one non-polymeric amphiphile exhibited smectic A mesophases. Another non-polymeric amphiphile exhibited a cholesteric mesophase. Thus, examples were found of amphitropic polymers and non-polymeric amphiphiles which can form organised molecular arrangements both because they are amphiphilic and because they contain mesogens.