2α,3α-dihydroxy-5α-pregnane-6,20-dione | 85764-18-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2α,3α-dihydroxy-5α-pregnane-6,20-dione
• 英文别名: (2R,3S)-2,3-dihydroxy-5α-pregnane-6,20-dione；(2R,3S,5S,8S,9S,10R,13S,14S,17S)-17-acetyl-2,3-dihydroxy-10,13-dimethyl-1,2,3,4,5,7,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-6-one
• CAS: 85764-18-7
• 化学式: C₂₁H₃₂O₄
• 分子量: 348.483
• InChiKey: YAZBDIHGYYUGOW-OECPUXPGSA-N

物化性质

• 沸点：
  488.3±45.0 °C(predicted)
• 密度：
  1.177±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.75
• 重原子数：
  25.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  74.6
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2α,3α-dihydroxy-5α-pregnane-6,20-dione 在 lithium tri(t-butoxy)aluminum hydride 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以61%的产率得到(20R)-2α,3α,20-trihydroxy-5α-pregnan-6-one
  参考文献：
  名称：

  Brassinosteroids with Ester Function with Five Carbon Atoms at the 20 Position

  摘要：

  已经合成了具有20位五个碳原子的酯基功能的油菜素和角鲨醇的孕烷类似物。在豆科植物的第二个节间生物测定中测试时，最有效的物质是VIII。

  DOI：

  10.1135/cccc19921731
• 作为产物：
  描述：

  6β-hydroxy-3α,5α-cyclo-pregnan-20-one 在 四氧化锇 、 水 、 铬酸 、 对甲苯磺酸 、 N-甲基吗啉氧化物 作用下， 以 环丁砜 、 丙酮 、 叔丁醇 为溶剂， 反应 1.67h， 生成 2α,3α-dihydroxy-5α-pregnane-6,20-dione
  参考文献：
  名称：

  Brassinolide and its analogs. Part IV. Synthesis of brassinolide analogs with or without the steroidal side chain.

  摘要：

  从胆固醇、豆甾醇或孕烯醇酮出发，合成了四种黄铜内酯类似物。在对水稻秧苗进行片层倾斜试验时，一种在 C-17 处具有羟基而不是甾体侧链的类似物的活性只有黄铜内酯的 0.001%，而其他类似物的活性是黄铜内酯的 1-2%。这表明侧链对黄铜内酯的植物生长促进活性起着不可或缺的作用。

  DOI：

  10.1271/bbb1961.47.97

文献信息

• Synthesis of Brassinosteroids of Varying Acyl Side Chains and Evaluation of Their Brassinolide-like Activity
  作者：Shinya UESUSUKI、Bunta WATANABE、Shuji YAMAMOTO、Junko OTSUKI、Yoshiaki NAKAGAWA、Hisashi MIYAGAWA

  DOI：10.1271/bbb.68.1097

  日期：2004.1

  Brassinosteroids containing various side chain moieties were synthesized and their activity was determined as the reciprocal logarithm of the ED50 (50% effective dose per plant in moles) in the rice lamina inclination assay using synergist indole-3-acetic acid (IAA). The introduction of a hydroxyl group in the α-position to the carbonyl group of the ester structure significantly enhanced the activity. 2α,3α-Dihydroxy-17β-[(2R,3S)-2-hydroxy-3-methylpentanoyl]oxy-B-homo-7-oxa-5α-androstan-6-one showed the highest activity, for which the pED50 was determined to be 10.5 under synergistic conditions with IAA. Under identical conditions, the pED50 values of brassinolide and castasterone were determined to be 13.6 and 12.3 respectively. With respect to the α-carbon of the acyl moiety, the R-form was 10 times more potent than the corresponding S-form. Substituting the terminal structure (Et) of the side chain to that of the most potent compound, brassinolide (i-Pr), did not increase the activity.

  含有各种侧链基团的油菜素内酯被合成，其活性通过米种叶片倾斜测定法中的50%有效剂量（以摩尔计算每株植物的ED50）的倒数对数来确定，使用协同剂吲哚-3-乙酸（IAA）。在酯结构的羰基的α位引入羟基显著增强了活性。2α,3α-二羟基-17β-[(2R,3S)-2-羟基-3-甲基戊酰氧]基-β-同源-7-氧-5α-雄甾-6-酮表现出最高的活性，在与IAA的协同作用下，其pED50被确定为10.5。在相同条件下，油菜素内酯和蒽醇的pED50值分别为13.6和12.3。就酰基的α碳而言，R型的效能是对应的S型的10倍。将侧链的末端结构（Et）替换为最强化合物油菜素内酯（i-Pr）的结构并没有增加活性。
• The introduction of a double bond on the steroid skeleton – The preparation of enol silyl ether derivatives from vicinal diols
  作者：Aleš Marek、Blanka Klepetářová、Tomáš Elbert

  DOI：10.1135/cccc2010145

  日期：——

  The ways of converting steroid vicinal diol into an unsaturated derivative were studied with the intention of preparing suitable precursors for the introduction of deuterium or tritium into the molecules of brassinosteroids. The model vicinal diol compound, 2α,3α-dihydroxy-5α-pregnane-6,20-dione (3), was converted with high regioselectivity to the α-hydroxy ketone derivative, 2α-hydroxy-5α-pregnane-3,6,20-trione (8), in a 75% yield. The attempts to convert α-hydroxy ketone 8 to the dioxolene derivative, 2α,3α-(isopropylidenedioxy)-5α-pregn-2-ene-6,20-dione (6), failed. The conditions for the conversion of ketone to the corresponding enol trialkylsilyl ether were optimized using cyclohexanone as a model compound. The best and reproducible results were obtained by using tert-butyldimethylsilyl trifluoromethansulfonate (TBDMSiOTf) as the silylating reagent and triethylamine as the base. Under these conditions, the 3,6,20-trione (8) was converted to 2,3-bis(tert-butyldimethylsilyloxy)-5α-pregn-2-ene-6,20-dione (14) with a 66% yield.

  将类固醇邻二醇转化为不饱和衍生物的方法进行了研究，目的是为了制备适合的前体，以将氘或氚引入油菜素类分子中。模型邻二醇化合物2α,3α-二羟基-5α-孕烷-6,20-二酮（3）以高区域选择性转化为α-羟基酮衍生物2α-羟基-5α-孕烷-3,6,20-三酮（8），产率为75%。尝试将α-羟基酮8转化为二氧杂环己烯衍生物2α,3α-(异丙基亚甲基二氧基)-5α-孕-2-烯-6,20-二酮（6）失败。使用环己酮作为模型化合物，优化了酮转化为相应烯醇三烷基硅醚的条件。使用叔丁基二甲基硅氧基三氟甲磺酸酯（TBDMSiOTf）作为硅化试剂，三乙胺作为碱，得到了最佳和可重复的结果。在这些条件下，3,6,20-三酮（8）以66%的产率转化为2,3-叔丁基二甲基硅氧基-5α-孕-2-烯-6,20-二酮（14）。
• Kohout, Ladislav; Velgova, Helena; Strnad, Miroslav, Collection of Czechoslovak Chemical Communications, 1987, vol. 52, # 2, p. 476 - 486
  作者：Kohout, Ladislav、Velgova, Helena、Strnad, Miroslav、Kaminek, Miroslav

  DOI：——

  日期：——