(8R,10R,13S,17S)-3,17-di(trimethylsilyloxy)-10,13-dimethyl-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthrene

• 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,10R,13S,17S)-3,17-di(trimethylsilyloxy)-10,13-dimethyl-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthrene
• 英文别名: (17β)-3,17-bis[(trimethylsilyl)oxy]androsta-2,4-diene；Testosterone (Androst-4-en-17B-ol-3-one), TMS；[(8R,9S,10R,13S,14S,17S)-10,13-dimethyl-3-trimethylsilyloxy-6,7,8,9,11,12,14,15,16,17-decahydro-1H-cyclopenta[a]phenanthren-17-yl]oxy-trimethylsilane
• 化学式: C₂₅H₄₄O₂Si₂
• 分子量: 432.794
• InChiKey: OGAHQMPXQGCDNO-OOPVGHQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.51
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1-diazo-2-ethoxy-2-oxoethyl)(2-(2-ethoxy-2-oxoethoxy)carbonylphenyl)iodonium trifluoromethanesulfonate 、 (8R,10R,13S,17S)-3,17-di(trimethylsilyloxy)-10,13-dimethyl-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthrene 在 sodium carbonate 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以44%的产率得到ethyl 2-diazo-2-((8R,10R,13S,17S)-10,13-dimethyl-3-oxo-17-((trimethylsilyl)oxy)-2,3,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-2-yl)acetate
  参考文献：
  名称：

  β-重氮羰基化合物：合成及其Rh（II）催化的1,3 CH插入

  摘要：

  本文中，我们描述了使用重氮甲基取代的高价碘试剂对酮甲硅烷基烯醇醚进行的首次亲电重氮甲基化，该试剂可访问不常见的β-重氮羰基化合物。通过发现罕见的Rh催化的分子内1,3 C-H卡宾插入导致复杂的环丙烷具有出色的立体控制，这一未开发的重氮化合物类在开发新反应中的潜力得到了证明。

  DOI：

  10.1002/anie.202015077
• 作为产物：
  描述：

  三甲基氯硅烷 、 睾酮 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 5.5h， 以80%的产率得到(8R,10R,13S,17S)-3,17-di(trimethylsilyloxy)-10,13-dimethyl-6,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthrene
  参考文献：
  名称：

  β-重氮羰基化合物：合成及其Rh（II）催化的1,3 CH插入

  摘要：

  本文中，我们描述了使用重氮甲基取代的高价碘试剂对酮甲硅烷基烯醇醚进行的首次亲电重氮甲基化，该试剂可访问不常见的β-重氮羰基化合物。通过发现罕见的Rh催化的分子内1,3 C-H卡宾插入导致复杂的环丙烷具有出色的立体控制，这一未开发的重氮化合物类在开发新反应中的潜力得到了证明。

  DOI：

  10.1002/anie.202015077

文献信息

• Detection of testosterone esters in human plasma
  作者：Xavier de la Torre、Jordi Segura、Aldo Polettini、Maria Montagna

  DOI：10.1002/jms.1190301004

  日期：1995.10

  The detection of testosterone misuse in sports is currently based on the urinary testosterone to epitestosterone ratio, although in some rare instances physiological or pathological conditions could compromise the application of this general criterion. The detection in the body of traces of the unchanged testosterone esters really ingested would offer unequivocal confirmation of testosterone administration. In this work, the detectability of testosterone esters in humans was studied. Liquid–liquid extraction of human blood plasma and appropriate derivatization of nine testosterone esters are described. Different acyl (trifluoroacetyl, pentafluoropropionyl and heptafluorobutyryl) and trimethylsilyl derivatives were studied. The trimethylsilyl derivatives appear to be the best for screenign purposes based on the characteristics of their mass spectra, with abundant molecular ions in the high-mass range. They also offered good conditions for tandem mass spectrometric analysis, needed to achieve the required sensitivity after oral administration of the drugs. The method was successful in the detection and determination of intramuscularly administered testosterone propionate and testosterone enanthate and orally ingested testosterone undecanoate.

  目前，检测体育运动中滥用睾酮的依据是尿液中睾酮与表睾酮的比率，但在某些罕见的情况下，生理或病理条件可能会影响这一一般标准的应用。如果能在体内检测到真正摄入的未改变的睾酮酯，就能明确证实睾酮的使用。在这项工作中，对人体中睾酮酯的可检测性进行了研究。研究描述了人体血浆的液液萃取和九种睾酮酯的适当衍生化过程。研究了不同的酰基（三氟乙酰基、五氟丙酰基和七氟丁酰）和三甲基硅基衍生物。根据其质谱特点，三甲基硅烷衍生物在高质范围内具有丰富的分子离子，似乎最适合用于筛选。它们还为串联质谱分析提供了良好的条件，而串联质谱分析是口服药物后达到所需灵敏度所必需的。该方法成功地检测和测定了肌肉注射的丙酸睾酮和庚酸睾酮以及口服的十一酸睾酮。
• Metabolism of anabolic steroids in humans: Synthesis of 6β-hydroxy metabolites of 4-chloro-1,2-dehydro-17α-methyltestosterone, fluoxymesterone, and metandienone
  作者：Willi Schänzer、Steve Horning、Manfred Donike

  DOI：10.1016/0039-128x(95)00008-e

  日期：1995.4

  Hydroxylation at position 6 beta of testosterone I (17 beta-hydroxyandrost-4-en-3-one) and the anabolic steroids 17 alpha-methyltestosterone II (17 beta-hydroxy-17 alpha-methylandrost-4-en-3-one), metandienone III (17 beta-hydroxy-17 alpha-methylandrosta-1, ,4-dien-3-one), 4-chloro-1,2-dehydro-17 alpha-methyltestosterone IV (4-chloro-17 beta-hydroxy-17 alpha-methylandrosta-1 ,4-dien-3-one), and fluoxymesterone V (9-fluoro-11 beta, 17 beta-dihydroxy-17 alpha-methylandrost-4-en-3-one) was achieved via light-induced autooxidation of the corresponding trimethylsilyl 3,5-dienol ethers dissolved in isopropanol or ethanol. The reaction further yielded the 6 alpha-hydroxy isomer in low amounts. The 6 beta-hydroxy isomers of I-V and the 6 alpha-hydroxy isomers of I, III, and IV were isolated and characterized by H-1 and C-13 NMR, high-performance liquid chromatography, gas chromatography, and mass spectrometry. Human excretion studies with single administered doses of boldenone (17 beta-hydroxyandrosta-1,4-dien-3-one), 4-chloro-1,2 -dehydro-17 alpha-methyltestosterone, fluoxymesterone, metandienone, 17 alpha-methyltestosterone, and [16, 16, 17-H-2(3)]testosterone showed that 6 beta-hydroxylation is the major metabolic pathway in the metabolism of 4-chloro-1,2-dehydro-17 alpha-methyltestosterone, fluoxymesterone, and metandienone, whereas for boldenone, 17 alpha-methyltestosterone, and testosterone, 6 beta-hydroxylation is negligable.
• β‐Diazocarbonyl Compounds: Synthesis and their Rh(II)‐Catalyzed 1,3 C−H Insertions
  作者：Liyin Jiang、Zhaofeng Wang、Melanie Armstrong、Marcos G. Suero

  DOI：10.1002/anie.202015077

  日期：2021.3.8

  of ketone silyl enol ethers with diazomethyl‐substituted hypervalent iodine reagents that gives access to unusual β‐diazocarbonyl compounds. The potential of this unexplored class of diazo compounds for the development of new reactions was demonstrated by the discovery of a rare Rh‐catalyzed intramolecular 1,3 C−H carbene insertion that led to complex cyclopropanes with excellent stereocontrol.

  本文中，我们描述了使用重氮甲基取代的高价碘试剂对酮甲硅烷基烯醇醚进行的首次亲电重氮甲基化，该试剂可访问不常见的β-重氮羰基化合物。通过发现罕见的Rh催化的分子内1,3 C-H卡宾插入导致复杂的环丙烷具有出色的立体控制，这一未开发的重氮化合物类在开发新反应中的潜力得到了证明。