(3alpha,5beta)-3,17-二羟基-孕甾烷-11,20-二酮 | 641-78-1

• 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
• 中文名称: (3alpha,5beta)-3,17-二羟基-孕甾烷-11,20-二酮
• 英文名称: 3α,17-dihydroxy-5β-pregnane-11,20-dione
• 英文别名: 3α,17α-dihydroxy-5β-pregnane-11,20-dione；5β-pregnane-3α,17α-diol-11,20-dione；3α,17-Dihydroxy-5β-pregnan-11,20-dion；3α.17-Dihydroxy-5β-pregnandion-(11.20)；Pregnane-3alpha,17alpha-diol-11,20-dione；(3R,5R,8S,9S,10S,13S,14S,17R)-17-acetyl-3,17-dihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,12,14,15,16-dodecahydro-1H-cyclopenta[a]phenanthren-11-one
• CAS: 641-78-1
• 化学式: C₂₁H₃₂O₄
• 分子量: 348.483
• InChiKey: AYEXSTRNLGYBSQ-YOBHSKELSA-N

物化性质

• 熔点：
  202-206°C
• 溶解度：
  可溶于氯仿、甲醇

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  25
• 可旋转键数：
  1
• 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
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3alpha,5beta)-3,17-二羟基-孕甾烷-11,20-二酮 在 吡啶 、 chromium(VI) oxide 、 溶剂黄146 作用下， 生成 3α-acetoxy-5β-androstanedione-(11.17)
  参考文献：
  名称：

  Partial Synthesis of Compounds Related to Adrenal Cortical Hormones. XVI. Preparation of Cortisone and Related Compounds¹

  摘要：

  DOI：

  10.1021/ja01122a060
• 作为产物：
  描述：

  (17Ξ)-3α,11,20-triacetoxy-5β-pregna-9(11),17(20)-diene 在 过氧化氢苯甲酰 、 苯 作用下， 生成 (3alpha,5beta)-3,17-二羟基-孕甾烷-11,20-二酮
  参考文献：
  名称：

  Preparation and Reactions of Steroidal Δ^17,(20)-Enol Acetates

  摘要：

  DOI：

  10.1021/ja01632a031

文献信息

• Structural requirements in 20-oxo-steroids for interaction with the catalytic site of 20.BETA.-hydroxysteroid dehydrogenase.
  作者：TAKAO HAYAKAWA、TSUYOSHI TANIMOTO、JIRO KAWAMURA

  DOI：10.1248/cpb.28.730

  日期：——

  Kinetic measurements were made to investigate the interaction of 20β-hydroxysteroid dehydrogenase and a series of steroids with C-17 and/or C-21 hydroxyl groups, and the role of the region around C-17 and C-21 on the interaction of the reacting 20-oxo group with the catalytic site of the enzyme was considered. Substitution of a hydroxyl group for hydrogen at C-21 of 17-deoxy-steroid derivatives caused a significant decrease in the apparent Vmax value (to about one-sixth to one-ninth), but a slight increase in the apparent Km value (about 1.1- to 1.8-fold). The same change at C-21 of 17-hydroxy-steroid derivatives caused little or no decrease in the apparent Vmax value, but an increase in the apparent Km (about 1.4- to 1.8-fold) occurred which was similar to that with 17-deoxy-steroid derivatives. In 21-deoxy-11-deoxy-steroid derivatives, a 17α-hydroxyl substituent had little effect on the apparent Km value (about 0.8- to 1.1-fold) and produced a slight decrease in the apparent Vmax value (to about three-quarters to two-fifths). Introduction of a 17α-hydroxyl group into 21-deoxy-11-oxo-steroid derivatives led to a significant decrease in the apparent Km value (to about one-seventh) and a moderate decrease in the apparent Vmax value (to about five-sixths to one-half). Introduction of a 17α-hydroxyl group into 21-hydroxy-steroid derivatives caused the apparent Vmax value to increase by about 1.8- to 11-fold, but caused little or no decrease in the apparent Km value. These results suggest that the hydroxyl group at the 21- or 17α-position directly restricted the conformation and the orientation of the 20-oxo group towards the catalytic site of the enzyme and influenced the hydrogen transfer stage in the catalytic process, and also that, of the substituents at the 21- and 17α-positions, the latter may preferentially affect the reaction efficiency of the 20-oxo group. The presence of an oxo group at C-11 had an indirect influence on the effects of the substituents at the 21- and 17α-positions. The optimum orientation of the 20-oxo group for the catalytic reaction may occur in 21-deoxy-17-deoxy-11-deoxy-steroid derivatives. In an ideal ternary complex, the 20-oxo group of the steroid may project towards the β-face of the steroid ring and the conformation between the 20-oxo group and α-hydrogen of C-17 is nearly staggered, while that between C-21 and the α-hydrogen of C-17, looking along the C-17 to C-20 axis, is in a skew form ; the 20-oxo group is orientated rather far from the methyl group at the β-position of C-13 and more towards the β-chain of C-16.

  进行了动力学测量，以研究20β-羟类固醇脱氢酶与一系列具有C-17和/或C-21羟基的类固醇之间的相互作用，并考虑了C-17和C-21附近区域对反应的20-氧基与酶催化位点相互作用的影响。将C-21的氢替换为羟基的17-脱氧类固醇衍生物导致表观Vmax值显著下降（降至约六分之一到九分之一），但表观Km值略微增加（约1.1到1.8倍）。在17-羟基类固醇衍生物的C-21处进行相同的改变对表观Vmax值几乎没有或没有造成下降，但表观Km值却增加（约1.4到1.8倍），这与17-脱氧类固醇衍生物的变化相似。在21-脱氧-11-脱氧类固醇衍生物中，17α-羟基取代体对表观Km值影响不大（约0.8到1.1倍），并导致表观Vmax值轻微下降（降至约三分之四到五分之二）。在21-脱氧-11-氧基类固醇衍生物中引入17α-羟基使表观Km值显著降低（降至约七分之一），而表观Vmax值中度下降（降至约五分之六到一半）。在21-羟基类固醇衍生物中引入17α-羟基使表观Vmax值增加约1.8到11倍，但对表观Km值几乎没有影响。这些结果表明，位于21或17α位点的羟基直接限制了20-氧基与酶催化位点之间的构象和取向，并影响了催化过程中的氢转移阶段。此外，在21和17α位点的取代基中，后者可能更优先影响20-氧基的反应效率。C-11的氧基的存在对21和17α位点取代基的影响具有间接作用。20-氧基在催化反应中的最佳取向可能发生在21-脱氧-17-脱氧-11-脱氧类固醇衍生物中。在一个理想的三元复合物中，类固醇的20-氧基可能朝向类固醇环的β面突出，且20-氧基与C-17的α-氢之间的构象几乎呈交错状态；而C-21与C-17的α-氢之间的角度在C-17至C-20轴上是倾斜的；20-氧基在空间上较远离C-13的β位甲基，更靠近C-16的β链。
• Chemical Studies with 11-Oxygenated Steroids. VII. The Oxidation of 3-Hydroxysteroids with t-Butyl Hypochlorite
  作者：G. S. Fonken、J. L. Thompson、R. H. Levin

  DOI：10.1021/ja01606a054

  日期：1955.1
• A New Method for the Preparation of 17(α)-Hydroxy-20-ketopregnanes
  作者：Lewis H. Sarett

  DOI：10.1021/ja01184a047

  日期：1948.4
• 11-Oxygenated Steroids. III. The Preparation of 11β-Hydroxy Pregnanes¹
  作者：Eugene P. Oliveto、Temple Clayton、E. B. Hershberg

  DOI：10.1021/ja01098a508

  日期：1953.1
• Enolates of 21-formyl steroids and process
  申请人：UPJOHN CO

  公开号：US02767198A1

  公开（公告）日：1956-10-16