17-O-tert-butyldimethylsilylestradiol

• 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: 17-O-tert-butyldimethylsilylestradiol
• 英文别名: (8R,9S,13S,14S,17S)-17-((tert-butyldimethylsilyl)oxy)-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-ol；17-((tert-butyldimethylsilyl)oxy)-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-ol；(8R,9S,13S,14S)-17-(tert-butyldimethylsilyloxy)-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-ol；(8R,9S,13S,14S,17S)-17-[tert-butyl(dimethyl)silyl]oxy-13-methyl-6,7,8,9,11,12,14,15,16,17-decahydrocyclopenta[a]phenanthren-3-ol
• 化学式: C₂₄H₃₈O₂Si
• 分子量: 386.65
• InChiKey: DLNJQUUCGTVWDU-NTYLBUJVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.64
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  17-O-tert-butyldimethylsilylestradiol 在 2-双环己基膦-2',6'-二甲氧基联苯 、 4-二甲氨基吡啶 、 potassium phosphate 、 palladium diacetate 、 三乙胺 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 水 为溶剂， 反应 5.0h， 生成 tert-butyldimethyl(((8R,9S,13S,14S,17S)-13-methyl-3-vinyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-17-yl)oxy)silane
  参考文献：
  名称：

  通过甲硅烷基二氟甲磺酸酯的甲硅烷基-赫克反应制备乙烯基甲硅烷基醚和二硅氧烷

  摘要：

  现在可以使用甲硅烷基-Heck 反应从芳基取代的烯烃和相关底物制备乙烯基甲硅烷基醚和二硅氧烷。该反应采用市售的催化剂体系和温和的条件。这项工作代表了一种非常实用的方法，可以以有效和直接的方式获得不同类别的乙烯基甲硅烷基醚底物，并具有完全的区域异构和几何选择性。

  DOI：

  10.1021/ja407748z
• 作为产物：
  描述：

  雌二醇 在 咪唑 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 生成 17-O-tert-butyldimethylsilylestradiol
  参考文献：
  名称：

  通过甲硅烷基二氟甲磺酸酯的甲硅烷基-赫克反应制备乙烯基甲硅烷基醚和二硅氧烷

  摘要：

  现在可以使用甲硅烷基-Heck 反应从芳基取代的烯烃和相关底物制备乙烯基甲硅烷基醚和二硅氧烷。该反应采用市售的催化剂体系和温和的条件。这项工作代表了一种非常实用的方法，可以以有效和直接的方式获得不同类别的乙烯基甲硅烷基醚底物，并具有完全的区域异构和几何选择性。

  DOI：

  10.1021/ja407748z

文献信息

• Visible Light-Induced Borylation of C–O, C–N, and C–X Bonds
  作者：Shengfei Jin、Hang. T. Dang、Graham C. Haug、Ru He、Viet D. Nguyen、Vu T. Nguyen、Hadi D. Arman、Kirk S. Schanze、Oleg V. Larionov

  DOI：10.1021/jacs.9b12519

  日期：2020.1.22

  photocatalytic borylation method that can effect borylation of a wide range of substrates, including strong C‒O bonds, remains elusive. Herein, we report a general, metal-free visible light-induced photocatalytic borylation platform that enables borylation of electron rich derivatives of phenols and anilines, chloroarenes, as well as other haloarenes. The reac-tion exhibits excellent functional group

  硼酸是中心重要的功能基序和合成前体。可见光诱导的硼酸化可以提供结构多样化的硼酸盐，但一种广泛有效的光催化硼酸化方法可以影响包括强 C-O 键在内的多种底物的硼化，仍然难以实现。在此，我们报告了一种通用的、无金属的可见光诱导光催化硼化平台，该平台能够对苯酚和苯胺、氯芳烃以及其他卤代芳烃的富电子衍生物进行硼化。该反应表现出优异的官能团耐受性，正如一系列结构复杂底物的硼化反应所证明的那样。值得注意的是，该反应是由吩噻嗪催化的，这是一种简单的有机光催化剂，MW< 200通过质子耦合电子转移机制介导了以前无法实现的可见光诱导的苯酚衍生物单电子还原，还原电位为~-3 V vs SCE。机理研究指出了光催化剂-碱相互作用的关键作用。
• (Arene)Cl2Ru(II) complexes with N-coordinated estrogen and androgen isonicotinates: Interaction with sex hormone binding globulin and anticancer activity
  作者：Rainer Schobert、Sebastian Seibt、Katharina Effenberger-Neidnicht、Caroline Underhill、Bernhard Biersack、Geoffrey L. Hammond

  DOI：10.1016/j.steroids.2010.12.009

  日期：2011.3

  (Arene)dichloridoruthenium(II) complexes with N-coordinated isonicotinates of androgens (6) and estrogens (9) were prepared and tested for affinity to the estrogen receptor (ER alpha) and sex hormone binding globulin (SHBG), as well as for cytotoxicity in cancer cells. None of the new complexes bound noticeably to the ER and most of them also bound less strongly to SHBG than the corresponding unmetallated steroids 7. In MTT assays the Ru(p-cymene) complexes 9 of 2-substituted estrones were equally or even more cytotoxic than the metal-free steroids against hormone-dependent (MCF-7 breast and KB-V1 cervix carcinomas) and hormone-independent (518A2 melanoma) cells. The addition of external SHBG to MU assays lowered the cytotoxicities of the complexes 9 and distinctly more so those of some steroids 7, probably by the way of sequestration and reduction of the cellular uptake. In the absence of SHBG the estrogen complexes 9 were internalized by 518A2 melanoma cells and ruthenated their DNA as quantified by ICP-OES. They also ruthenated salmon sperm DNA but did not change the topology of plasmid DNA in EMSA experiments. In addition, the Ru(p-cymene) complex of 2-ethoxyestrone (9c) was shown to reduce the motility of 518A2 melanoma cells in a wound-healing assay. (C) 2010 Elsevier Inc. All rights reserved.

  (arene)二氯化二钌(II)复合物与N-配位的雄激素（6）和雌激素（9）的异烟酸酰胺衍生物已被制备，并测试了其对雌激素受体（ERα）和性激素结合球蛋白（SHBG）的亲和力以及在癌细胞中的细胞毒性。新的复合物均未明显结合ER，且其中大多数与SHBG的结合力亦弱于相应的无金属甾体（7）。在MTT实验中，2-取代雌酮的Ru(p-甲乙基环己二烯)复合物（9）对激素依赖性（MCF-7乳腺癌和KB-V1宫颈癌）及激素非依赖性（518A2黑色素瘤）细胞的毒性与金属无甾体相当甚至更高。在加入外源性SHBG至HU实验中，其对复合物9的细胞毒性有所降低，且对某些甾体（7）的降低明显，可能是通过屏蔽及减少胞内摄取的途径实现。在无SHBG的情况下，雌激素复合物9被518A2黑色素瘤细胞摄入，并以ICP-OES定量其DNA的钌化修饰。它们亦能钌化鲑鱼精子DNA，但在EMSA实验中未改变质粒DNA的拓扑结构。此外，2-乙氧雌酮的Ru(p-甲乙基环己二烯)复合物（9c）在划痕修复实验中被证实可显著降低518A2黑色素瘤细胞的迁移能力。（C）2010 Elsevier Inc. 保留所有权利。
• Mild base mediated desilylation of various phenolic silyl ethers
  作者：Noel S. Wilson、Brian A. Keay

  DOI：10.1016/s0040-4039(96)02270-8

  日期：1997.1

  A variety of phenolic silyl ethers are easily desilylated in good to excellent yields by treatment with 1.1 equivalents of K2CO3, and ethanol containing 5 equivalents of water.

  通过用1.1当量的K 2 CO 3和含5当量的水的乙醇处理，各种酚类甲硅烷基醚很容易被甲硅烷基化，产率高至优异。
• Demethylaromatization of cyclohexadienones by iodotriphenylphosphonium iodide
  作者：Guanghui Chen、Yong Shi、Weisheng Tian、Hongyan Xie、Zhaohua Yan、Junmin Yu

  DOI：10.1016/j.tetlet.2023.154365

  日期：2023.3

  A highly efficient and metal-free demethylation and concomitant aromatization of cyclohexadienones using iodotriphenylphosphonium iodide was developed. A variety of steroidal and non-steroidal substrates smoothly underwent demethylaromatization reaction generating the corresponding phenolic products in good yields. This approach exhibits broad functional group tolerance. An ionic mechanism of synergistic

  开发了使用碘化三苯基磷碘化物对环己二烯酮进行高效且无金属的去甲基化和伴随的芳构化。多种甾体和非甾体底物顺利进行去甲基芳构化反应，以良好的收率生成相应的酚类产物。这种方法表现出广泛的功能组耐受性。提出了协同作用的离子机制。该方法在 1,4-androstadiene-3,17-dione 一步转化为 3-hydroxy-1,3,5(10)-estratrien-17-one 过程中显示出潜在的工业价值一系列甾体避孕药。
• Generation of Arynes via Ate Complexes of Arylboronic Esters with an <i>ortho</i>-Leaving Group
  作者：Yuto Sumida、Tomoe Kato、Takamitsu Hosoya

  DOI：10.1021/ol401140d

  日期：2013.6.7

  An efficient method of generating aryne has been achieved by treating ortho-(trifluoromethanesulfonyloxy)arylboronic acid pinacol ester with tert-or sec-butyllithium. Monitoring the reaction by B-11 NMR has indicated that a boron-ate complex formed in situ is the eventual precursor that converts into aryne near room temperature. The prior formation of the ate complex at a low temperature has enabled us to use various arynophiles, including those bearing base-sensitive groups. The ready availability of the aryne precursors and mutual orthogonality in aryne generation with widely used ortho-silylaryl triflate have enhanced the utility of the method.