17-((tert-butyldimethylsilyl)oxy)-10,13-dimethylhexadecahydro-3H-cyclopenta[a]phenanthren-3-one | 58701-44-3

• 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: 17-((tert-butyldimethylsilyl)oxy)-10,13-dimethylhexadecahydro-3H-cyclopenta[a]phenanthren-3-one
• 英文别名: 17β-[(tert-butyldimethylsilyl)oxy]-5α-androstan-3-one；17β-t-Butyldimethylsilyloxy-5α-androstan-3-one；17β-(tert-Butyldimethylsiloxy)androstan-3-one；androstanolone t-butyldimethylsilyl ether；17β-TBDMS-dihydrotestosterone；17β-[(Tert-butyldimethylsilyl)oxy]-5α-androstane-3-one；(5S,8R,9S,10S,13S,14S,17S)-17-((Tert-butyldimethylsilyl)oxy)-10,13-dimethyltetradecahydro-1H-cyclopenta[A]phenanthren-3(2H)-one；(5S,8R,9S,10S,13S,14S,17S)-17-[tert-butyl(dimethyl)silyl]oxy-10,13-dimethyl-1,2,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-3-one
• CAS: 58701-44-3
• 化学式: C₂₅H₄₄O₂Si
• 分子量: 404.709
• InChiKey: BDIJWGREUGQQQQ-PJJIPRPHSA-N

物化性质

• 沸点：
  448.2±38.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.99
• 重原子数：
  28
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  17-((tert-butyldimethylsilyl)oxy)-10,13-dimethylhexadecahydro-3H-cyclopenta[a]phenanthren-3-one 在 盐酸 作用下， 以 乙醇 为溶剂， 反应 3.0h， 以97.5%的产率得到雄诺龙
  参考文献：
  名称：

  A new simple and high-yield synthesis of 5α-dihydrotestosterone (DHT), a potent androgen receptor agonist

  摘要：

  We have devised an efficient procedure for the synthesis of 5 alpha-dihydrotestosterone (DHT) (1) starting from 3 beta-hydroxy-5 alpha-androstan-17-one, providing the product in unprecedented 82% yield. A reported method of using toxic Jones reagent is replaced by milder oxidizing agent (NMO/TPAP) in the synthesis of a key intermediate 17 beta-[(tert-butyldimethylsilyl)oxy]-5 alpha-androstan-3-one (18). This new procedure is simple, does not require special apparatus/precautions or chromatographic purification in most of the steps. (c) 2012 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2012.09.003
• 作为产物：
  描述：

  3-乙酰基-5Α-雄烷二醇 在 咪唑 、 四丙基高钌酸铵 、 N-甲基吗啉氧化物 、 potassium hydroxide 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.33h， 生成 17-((tert-butyldimethylsilyl)oxy)-10,13-dimethylhexadecahydro-3H-cyclopenta[a]phenanthren-3-one
  参考文献：
  名称：

  A new simple and high-yield synthesis of 5α-dihydrotestosterone (DHT), a potent androgen receptor agonist

  摘要：

  We have devised an efficient procedure for the synthesis of 5 alpha-dihydrotestosterone (DHT) (1) starting from 3 beta-hydroxy-5 alpha-androstan-17-one, providing the product in unprecedented 82% yield. A reported method of using toxic Jones reagent is replaced by milder oxidizing agent (NMO/TPAP) in the synthesis of a key intermediate 17 beta-[(tert-butyldimethylsilyl)oxy]-5 alpha-androstan-3-one (18). This new procedure is simple, does not require special apparatus/precautions or chromatographic purification in most of the steps. (c) 2012 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2012.09.003

文献信息

• Dehydroxymethylation of Alcohols Enabled by Cerium Photocatalysis
  作者：Kaining Zhang、Liang Chang、Qing An、Xin Wang、Zhiwei Zuo

  DOI：10.1021/jacs.9b05932

  日期：2019.7.3

  functionality has been reliably transferred into nucleophilic radicals with the loss of one molecule of formaldehyde. Intriguingly, we found that the dehydroxymethylation process can be significantly promoted by the cerium catalyst, and the stabilization effect of the fragmented radicals also plays a significant role. This operationally simple protocol has enabled the direct utilization of primary alcohols as unconventional

  脱羟甲基化是将醇原料直接转化为少一个碳原子的烷基合成子，是一种利用醇材料的普遍性和稳健性的非常规且未充分探索的策略。在温和且氧化还原中性的反应条件下，利用廉价的铈催化剂，提供了光催化脱羟甲基化平台。通过配体到金属的电荷转移催化，醇官能团已可靠地转移到亲核自由基中，同时失去一分子甲醛。有趣的是，我们发现铈催化剂可以显着促进脱羟甲基化过程，并且碎片自由基的稳定作用也起着重要作用。这种操作简单的方案能够直接利用伯醇作为非常规烷基亲核试剂，用于自由基介导的 1,4-共轭加成与迈克尔受体。广泛的醇类，从简单的乙醇到复杂的核苷和类固醇，已成功应用于这种片段偶联转化。此外，该催化系统的模块化已在多种自由基介导的转化中得到证实，包括氢化、胺化、烯基化和氧化。
• Construction of a quaternary carbon at the carbonyl carbon of the cyclohexane ring
  作者：Yuki Kaneko、Yohei Kiyotsuka、Hukum P. Acharya、Yuichi Kobayashi

  DOI：10.1039/c0cc00653j

  日期：——

  High S(N)2' selectivity in the allylic substitution of cyclohexylidene ethyl picolinates with copper reagents prepared from RMgBr and CuBr.Me(2)S was realized by addition of ZnX(2) (X = I, Br, Cl). Furthermore, ZnX(2) accelerated the reaction with the bulky iPr reagent.

  通过添加ZnX（2）（X = I，Br，Cl）实现了用RMgBr和CuBr.Me（2）S制备的铜试剂对环己叉基乙基吡啶甲酸乙酯进行烯丙基取代的高S（N）2'选择性。此外，ZnX（2）促进了与庞大的iPr试剂的反应。
• Ligand-Free Iron-Catalyzed Carbon (sp²)–Carbon (sp²) Oxidative Homo-Coupling of Alkenyllithiums
  作者：Zhuliang Zhong、Zhi-Yong Wang、Shao-Fei Ni、Li Dang、Hung Kay Lee、Xiao-Shui Peng、Henry N. C. Wong

  DOI：10.1021/acs.orglett.8b03893

  日期：2019.2.1

  and hexa-substituted 1,3-butadienes. This one-pot procedure involves lithium–iodine exchange to generate the corresponding vinyllithium intermediates. A subsequent iron-catalyzed ligand-free oxidative homo-coupling eventually led to the formation of 1,3-butadienes in acceptable to excellent isolated yields.

  为了有效合成二，四和六取代的1，3-丁二烯，开发了一种新的策略。这一一锅法涉及锂碘交换，以生成相应的乙烯基锂中间体。随后的铁催化的无配体的氧化均偶联最终导致以可接受的分离出的优良收率形成1，3-丁二烯。
• O-Methoxycarbonyl Cyanohydrin as a New Protective Group for Carbonyls
  作者：David Berthiaume、Donald Poirier

  DOI：10.1016/s0040-4020(00)00535-4

  日期：2000.8

  O-Methoxycarbonyl cyanohydrin, a new protective group of carbonyls, was prepared in high yields by an efficient one-step procedure using methyl cyanoformate and a secondary alkylamine at room temperature. Herein, we report efficient methods for the formation and cleavage of the protective group. Also, the ability of different types of carbonyls to be protected and the protective group's behavior under different

  通过高效的一步法，在室温下使用氰基甲酸酯甲酯和仲烷基胺，高产率地制备了O-甲氧羰基氰醇，一种新的羰基保护基团。在此，我们报道了形成和裂解保护基的有效方法。此外，研究了不同类型的羰基被保护的能力以及保护基在不同化学条件下的行为。
• Unexpected formation of <i>O</i>-methoxycarbonyl cyanohydrin showing potential as a protective group of ketones
  作者：Donald Poirier、David Berthiaume、Roch P. Boivin

  DOI：10.1055/s-1999-2859

  日期：1999.9

  A one-step procedure using methyl cyanoformate and a secondary alkylamine was reported to efficiently transform ketones into O-methoxycarbonyl cyanohydrins. This functional group shows interesting potential in protecting group chemistry.

  据报道，使用氰甲酸甲酯和二级烷基胺的一步法能高效地将酮转化为O-甲氧羰基氰醇。这一功能团在保护基化学中显示出有趣的潜在应用。