(8R,9S,13S,14S)-methyl 7,8,9,11,12,13,14,15,16,17-decahydro-3-methoxy-13-methyl-17-oxo-6H-cyclopenta[a]phenanthrene-16-carboxylate | 135682-91-6

• 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: (8R,9S,13S,14S)-methyl 7,8,9,11,12,13,14,15,16,17-decahydro-3-methoxy-13-methyl-17-oxo-6H-cyclopenta[a]phenanthrene-16-carboxylate
• 英文别名: estrone methyl ester；methyl (8R,9S,13S,14S)-3-methoxy-13-methyl-17-oxo-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthrene-16-carboxylate；methyl (8R,9S,13S,14S)-3-methoxy-13-methyl-17-oxo-7,8,9,11,12,14,15,16-octahydro-6H-cyclopenta[a]phenanthrene-16-carboxylate
• CAS: 135682-91-6
• 化学式: C₂₁H₂₆O₄
• 分子量: 342.435
• InChiKey: LSHBHSFAOXGHPP-JKHYUPIASA-N

物化性质

• 沸点：
  475.8±45.0 °C(Predicted)
• 密度：
  1.159±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (8R,9S,13S,14S)-methyl 7,8,9,11,12,13,14,15,16,17-decahydro-3-methoxy-13-methyl-17-oxo-6H-cyclopenta[a]phenanthrene-16-carboxylate 在 sodium tetrahydroborate 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Targeting RORs nuclear receptors by novel synthetic steroidal inverse agonists for autoimmune disorders

  摘要：

  Designing novel inverse agonists of NR ROR gamma t still represents a challenge for the pharmaceutical community to develop therapeutics for treating immune diseases. By exploring the structure of NRs natural ligands, the representative arotenoid ligands and RORs specific ligands share some chemical homologies which can be exploited to design a novel molecular structure characterized by a polycyclic core bearing a polar head and a hydrophobic tail. Compound MG 2778 (8), a cyclopenta[a]phenantrene derivative, was identified as lead compound which was chemically modified at position 2 in order to obtain a small library for preliminary SARs. Cell viability and estrogenic activity of compounds 7, 8, 19a, 30, 31 and 32 were evaluated to attest selectivity. The selected 7, 8, 19a and 31 compounds were assayed in a Gal4 UAS-Luc co-transfection system in order to determine their ability to modulate ROR gamma t activity in a cellular environment. They were evaluated as inverse agonists taken ursolic acid as reference compound. The potency of compounds was lower than that of ursolic acid, but their efficacy was similar. Compound 19a was the most active, significantly reducing ROR gamma t activity at low micromolar concentrations. (c) 2018 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2018.02.018
• 作为产物：
  描述：

  雌酚酮 在 sodium hydroxide 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 18.5h， 生成 (8R,9S,13S,14S)-methyl 7,8,9,11,12,13,14,15,16,17-decahydro-3-methoxy-13-methyl-17-oxo-6H-cyclopenta[a]phenanthrene-16-carboxylate
  参考文献：
  名称：

  通过扩环生成稠合七元多环系统及其在倍半萜类化合物全合成中的应用

  摘要：

  广泛存在于天然产物和分子药物中的七元多环结构是具有挑战性的合成靶标。然而，合成融合中型双环的方法[ m . n .0] 环系统，包括苯并环庚烷系统，仍然是紧迫的。在这里，我们将碱基诱导的环扩展描述为构建广泛的稠合七元环系统的一般策略。该方法的应用通过两种倍半萜类化合物 plecarpenene 和 plecarpenone 的高效全合成得到证明，两者均具有稠合的双环 [5.3.0] 癸烷骨架。

  DOI：

  10.1021/acs.orglett.2c01401

文献信息

• Chromium(II)-Catalyzed Diastereoselective and Chemoselective Csp²–Csp³ Cross-Couplings Using Organomagnesium Reagents
  作者：Jie Li、Qianyi Ren、Xinyi Cheng、Konstantin Karaghiosoff、Paul Knochel

  DOI：10.1021/jacs.9b08586

  日期：2019.11.13

  A simple protocol for performing chromium-catalyzed highly diastereoselective alkylations of arylmagnesium halides with cyclohexyl iodides at ambient temperature has been developed. Furthermore, this ligand-free CrCl2 enables efficient electrophilic alkenylations of primary, secondary and tetiary alkylmagnesium halides with readily available alkenyl acetates. Moreover, this chemoselective C‒C coupling

  已开发出一种在环境温度下用环己基碘对芳基镁卤化物进行铬催化的高度非对映选择性烷基化的简单方案。此外，这种不含配体的 CrCl2 能够使伯、仲和叔烷基卤化镁与容易获得的乙酸烯基酯进行有效的亲电烯基化。此外，这种与立体定义的烯基乙酸酯的化学选择性 C-C 偶联反应以立体保留方式进行。烷基碘化物和烯基乙酸酯上的各种官能团具有良好的耐受性，从而以良好的收率和高非对映选择性提供官能化的 Csp2-Csp3 偶联产物。详细的机理研究表明，原位生成的低价铬 (I) 物种可能是这些 Csp2-Csp3 交叉偶联的活性催化剂。
• Synthesis of α-Quaternary Bicyclo[1.1.1]pentanes through Synergistic Organophotoredox and Hydrogen Atom Transfer Catalysis
  作者：Jeremy Nugent、Alistair J. Sterling、Nils Frank、James J. Mousseau、Edward A. Anderson

  DOI：10.1021/acs.orglett.1c03346

  日期：2021.11.5

  Bicyclo[1.1.1]pentanes (BCPs) are important in drug design as sp3-rich bioisosteres of arenes and tert-butyl groups; however, the preparation of BCPs with adjacent quaternary carbons is barely known. We report a facile synthesis of α-quaternary BCPs using organophotoredox and hydrogen atom transfer catalysis in which α-keto radicals, generated through oxidation of β-ketocarbonyls, undergo efficient

  双环[1.1.1]戊烷 (BCP) 作为芳烃和叔丁基的富含sp 3 的生物电子等排体在药物设计中很重要；然而，具有相邻季碳的 BCP 的制备几乎不为人所知。我们报告了使用有机光氧化还原和氢原子转移催化轻松合成 α-四元 BCP，其中通过 β-酮羰基氧化产生的 α-酮自由基有效地添加到 [1.1.1] 丙烷中。BCP 产品可以转化为各种有用的衍生物，包括具有 α-四元立体中心的对映体富集的 BCP。
• Alkaline-Earth Metal Catalyzed Dehydrative Allylic Alkylation
  作者：Peizhong Xie、Shuangshuang Li、Yanan Liu、Xinying Cai、Jinyu Wang、Xiaobo Yang、Teck-Peng Loh

  DOI：10.1021/acs.orglett.9b03730

  日期：2020.1.3

  An alkaline-earth metal catalytic system for environmentally benign allylic alkylation was developed. Allylic alcohols can be utilized directly at room temperature in this transition-metal-free process, producing water as the only byproduct. A variety of allylic compounds, including the ones containing all-carbonyl quaternary centers, can be obtained with high yields.

  开发了一种碱土金属催化体系，用于环境友好的烯丙基烷基化反应。烯丙醇可在室温下直接用于这种无过渡金属的过程中，产生水作为唯一的副产物。可以高收率获得各种烯丙基化合物，包括含有全羰基季中心的烯丙基化合物。
• Catalyst-Controlled Regioselective Acylation of β-Ketoesters with α-Diazo Ketones Induced by Visible Light
  作者：Dan Liu、Wei Ding、Quan-Quan Zhou、Yi Wei、Liang-Qiu Lu、Wen-Jing Xiao

  DOI：10.1021/acs.orglett.8b03189

  日期：2018.11.16

  A catalyst-controlled acylation reaction of β-ketoesters was developed for the first time by combining visible-light photoactivation with Lewis acid or base catalysis. By employing a NiCl2·glyme complex with a bis(oxazoline) ligand as the Lewis acid catalyst, C-acylation products are exclusively achieved, while utilizing pyridine or DABCO as the Lewis base catalyst affords O-acylation products with

  通过将可见光光活化与路易斯酸或碱催化相结合，首次开发了β-酮酸酯的催化剂控制的酰化反应。通过使用具有双（恶唑啉）配体的NiCl 2 ·甘醇二甲醚络合物作为路易斯酸催化剂，可以独家获得C-酰化产物，同时使用吡啶或DABCO作为路易斯碱催化剂可得到O-具有完全区域选择性的酰化产物。一系列具有令人满意的结构多样性的β-酮酸酯适用于该转化，证明了该方法的官能团相容性，这归因于温和的反应条件。这种成功很大程度上建立在可见光引起的Wolff重排和独特的催化活化方式的基础上，因此，这项工作大大扩展了乙烯酮化学的应用。
• Characteristic Behavior of Chemisorbed Oxygen towards CO on Ag Surface
  作者：Kenzi Tamaru

  DOI：10.1246/cl.1999.577

  日期：1999.7

  When oxygen reacts with CO on Ag surface, the silver surface is fully coveed by oxygen, but only a limited part of the chemisorbed oxygen participates in the reaction. Such characteristic behavior was discussed on the basis of STM observation.

  当氧气与一氧化碳在银表面发生反应时，银表面完全被氧气覆盖，但只有有限的化学吸附氧参与反应。我们根据 STM 观察结果讨论了这种特征行为。