[(8R,9S,13S,14S)-3-[tert-butyl(dimethyl)silyl]oxy-13-methyl-6,7,8,9,11,12,14,15-octahydrocyclopenta[a]phenanthren-17-yl] trifluoromethanesulfonate | 400089-52-3

• 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)-3-[tert-butyl(dimethyl)silyl]oxy-13-methyl-6,7,8,9,11,12,14,15-octahydrocyclopenta[a]phenanthren-17-yl] trifluoromethanesulfonate
• CAS: 400089-52-3
• 化学式: C₂₅H₃₅F₃O₄SSi
• 分子量: 516.697
• InChiKey: JPUYAKMVZBJTPA-YOEKFXIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.29
• 重原子数：
  34
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  61
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [(8R,9S,13S,14S)-3-[tert-butyl(dimethyl)silyl]oxy-13-methyl-6,7,8,9,11,12,14,15-octahydrocyclopenta[a]phenanthren-17-yl] trifluoromethanesulfonate 在 四(三苯基膦)钯 、 四丁基氟化铵 、 lithium chloride 作用下， 以 四氢呋喃 为溶剂， 反应 26.0h， 生成 5-[(8S,9S,13S,14S)-3-hydroxy-13-methyl-6,7,8,9,11,12,14,15-octahydrocyclopenta[a]phenanthren-17-yl]pyran-2-one
  参考文献：
  名称：

  5-(Trimethylstannyl)-2H-pyran-2-one and 3-(Trimethylstannyl)-2H-pyran-2-one:  New 2H-Pyran-2-one Synthons

  摘要：

  5-(Trimethylstannyl)-2H-pyran-2-one (11) and 3-(trimethylstannyl)-2H-pyran-2-one (30), readily prepared from the corresponding bromo-2H-pyran-2-ones, undergo Pd(0)-catalyzed coupling reactions with a variety of enol triflates to give 5- and 3- substituted 2H-pyran-2-ones, respectively, This reaction is applicable to the enol triflates of 14 beta-hydroxy-17-ketosteroids, and therefore may prove useful in convergent syntheses of lucibufagins and bufadienolides.

  DOI：

  10.1021/jo951394t
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 咪唑 、 正丁基锂 、 二异丙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 生成 [(8R,9S,13S,14S)-3-[tert-butyl(dimethyl)silyl]oxy-13-methyl-6,7,8,9,11,12,14,15-octahydrocyclopenta[a]phenanthren-17-yl] trifluoromethanesulfonate
  参考文献：
  名称：

  5-(Trimethylstannyl)-2H-pyran-2-one and 3-(Trimethylstannyl)-2H-pyran-2-one:  New 2H-Pyran-2-one Synthons

  摘要：

  5-(Trimethylstannyl)-2H-pyran-2-one (11) and 3-(trimethylstannyl)-2H-pyran-2-one (30), readily prepared from the corresponding bromo-2H-pyran-2-ones, undergo Pd(0)-catalyzed coupling reactions with a variety of enol triflates to give 5- and 3- substituted 2H-pyran-2-ones, respectively, This reaction is applicable to the enol triflates of 14 beta-hydroxy-17-ketosteroids, and therefore may prove useful in convergent syntheses of lucibufagins and bufadienolides.

  DOI：

  10.1021/jo951394t

文献信息

• Palladium-Catalyzed Cross-Coupling Reaction of Bis(pinacolato)diboron with 1-Alkenyl Halides or Triflates:  Convenient Synthesis of Unsymmetrical 1,3-Dienes via the Borylation-Coupling Sequence
  作者：Jun Takagi、Kou Takahashi、Tatsuo Ishiyama、Norio Miyaura

  DOI：10.1021/ja0202255

  日期：2002.7.1

  1-alkenylboronic acid pinacol esters via a palladium-catalyzed cross-coupling reaction of bis(pinacolato)diboron (pin(2)B(2), pin = Me(4)C(2)O(2)) with 1-alkenyl halides or triflates was carried out in toluene at 50 degrees C in the presence of KOPh (1.5 equiv) and PdCl(2)(PPh(3))(2)-2Ph(3)P (3 mol %). The borylation of acyclic and cyclic 1-alkenyl bromides and triflates was achieved in high yields with complete

  通过钯催化的双（频哪醇）二硼（pin（2）B（2），pin = Me（4）C（2）O（2））的交叉偶联反应合成1-烯基硼酸频哪醇酯在 KOPh（1.5 当量）和 PdCl(2)(PPh(3))(2)-2Ph(3)P (3 mol%) 的存在下，1-烯基卤化物或三氟甲磺酸酯在 50 摄氏度的甲苯中进行。无环和环状 1-烯基溴化物和三氟甲磺酸酯的硼化反应以高产率实现，并完全保留了双键的构型。该方法通过硼酸化偶联序列应用于不对称1,3-二烯的一锅法合成。
• [EN] STEREOSELECTIVE SYNTHESIS OF 17-a -AND 17-ß -ARYL STEROIDAL COMPOUNDS<br/>[FR] SYNTHÈSE STÉRÉOSÉLECTIVE DE COMPOSÉS STÉROÏDES 17-? -ET 17-? -ARYLE
  申请人：SCRIPPS RESEARCH INST

  公开号：WO2009137337A1

  公开（公告）日：2009-11-12

  A process for forming one or the other of a 17-α-aryl or 17-β-aryl steroidal compound in diastereo excess is disclosed. The process utilizes a 17-keto steroid to form a Δ16-17-aryl-steroid compound or a 17-β-hydroxy-17-α-aryl steroid compound that are reduced or deoxygenated, respectively, in the presence of Raney nickel to form a 17-β-aryl- steroid or 17-α-aryl steroid, respectively, in a diastereo ratio of at least 3:1.

  公开了一种形成17-α-芳基或17-β-芳基类固醇化合物之一的过程，使得该过程利用17-酮类固醇形成Δ16-17-芳基类固醇化合物或17-β-羟基-17-α-芳基类固醇化合物，分别在Raney镍的存在下还原或脱氧，以形成17-β-芳基类固醇或17-α-芳基类固醇，其立体选择性比至少为3:1。
• Shi, Jun; Shigehisa, Hiroki; Guerrero, Carlos A., Angewandte Chemie - International Edition, 2009, vol. 48, p. 4328 - 4331
  作者：Shi, Jun、Shigehisa, Hiroki、Guerrero, Carlos A.、Shenvi, Ryan A.、Li, Chuang-Chuang、Baran, Phil S.

  DOI：——

  日期：——
• A Suzuki coupling approach to bufadienolides
  作者：Edward C Gravett、Philip J Hilton、Keith Jones、Fernando Romero

  DOI：10.1016/s0040-4039(01)01980-3

  日期：2001.12

  A high yielding route to bufadienolide type steroids using a novel Suzuki Coupling reaction between a range of steroid vinyl triflates and 2-pyrone-5-boronate 11 is presented. (C) 2001 Elsevier Science Ltd. All rights reserved.
• 5-(Trimethylstannyl)-2<i>H</i>-pyran-2-one and 3-(Trimethylstannyl)-2<i>H</i>-pyran-2-one:  New 2<i>H</i>-Pyran-2-one Synthons
  作者：Zhi Liu、Jerrold Meinwald

  DOI：10.1021/jo951394t

  日期：1996.1.1

  5-(Trimethylstannyl)-2H-pyran-2-one (11) and 3-(trimethylstannyl)-2H-pyran-2-one (30), readily prepared from the corresponding bromo-2H-pyran-2-ones, undergo Pd(0)-catalyzed coupling reactions with a variety of enol triflates to give 5- and 3- substituted 2H-pyran-2-ones, respectively, This reaction is applicable to the enol triflates of 14 beta-hydroxy-17-ketosteroids, and therefore may prove useful in convergent syntheses of lucibufagins and bufadienolides.