16β-chloro-3β,17α-dihydroxypregn-5-en-20-one | 17975-89-2

• 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: 16β-chloro-3β,17α-dihydroxypregn-5-en-20-one
• 英文别名: 1-[(3S,8R,9S,10R,13S,14S,16S,17R)-16-chloro-3,17-dihydroxy-10,13-dimethyl-1,2,3,4,7,8,9,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-17-yl]ethanone
• CAS: 17975-89-2
• 化学式: C₂₁H₃₁ClO₃
• 分子量: 366.928
• InChiKey: VWOWSZXVRFCHFR-OCHQKFOUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  25
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  16β-chloro-3β,17α-dihydroxypregn-5-en-20-one 在 copper(II) acetate monohydrate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 16β-chloro-3β,17α-dihydroxy-17β-methyl-17a-homoandrost-5-en-17a-one
  参考文献：
  名称：

  孕烷，雄甾烷和d-高雄甾烷的新型1,2,3-三唑基衍生物的合成。串联“点击”反应/ Cu催化的d - homo重排†

  摘要：

  铜催化的1，3-偶极环加成已用于甾族叠氮化物与各种末端炔的反应中。以高收率（70-98％）获得了许多新型的孕烷，雄烷酮和D-高雄甾烷的1,2,3-三唑基衍生物。尽管多环系统施加了空间位阻，但发达的合成方案使我们能够将三唑基部分直接连接到侧链和甾族骨架上。Cu（II）的存在显示出在温和条件下引起D-均质重排。合理选择铜预催化剂可以使我们与串联D一起进行“点击”反应-homo重排或在没有此过程的情况下。研究了在Cu（II）催化下16-杂取代的类固醇发生D- homo重排的趋势。

  DOI：

  10.1039/c4ob00404c
• 作为产物：
  描述：

  16,17-环氧孕烯醇酮 在 盐酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 16β-chloro-3β,17α-dihydroxypregn-5-en-20-one
  参考文献：
  名称：

  Selektive Addition von gasf�rmigem Chlorwasserstoff an kristalline Epoxide und Steroid-Epoxide

  摘要：

  Solid epoxides add gaseous HCl or HBr regioselectively and without melting, if the melting points are sufficiently high. Such additions proceed diastereoselectively with chiral epoxides. These gas/solid reactions are compared to similar transformations in solution. One observes interesting reaction sequences in the conversions of steroidal epoxides. Thus, the opening of the epoxide ring may be followed by cationic rearrangements, or it occurs elimination of water, if it creates conjugation to a carbonyl group.

  DOI：

  10.1002/prac.19923340503

文献信息

• Highly efficient Lewis acid catalyzed, one step conversions of 16α,17α-epoxy-3β-hydroxypregn-5-en-20-one to d-homosteroid and Δ13-steroids
  作者：Navdeep K Girdhar、M.P.S Ishar、Rajiv Kumar、Rajinder Singh、Gurmit Singh

  DOI：10.1016/s0040-4020(01)00673-1

  日期：2001.8

  Conversion of 16 alpha ,17 alpha -epoxy-3 beta -hydroxypregn-5-en-20-one (1a) to 16 beta -chloro-3 beta ,17 alpha -dihydroxy-17 beta -methyl-17a-homoandrost-5-en-17a-one (3) in very high yields (95%), in one step by treatment with 3 equiv. of anhyd. AlCl3, has been achieved; use of two equiv. of AlCl3 affords mixture Of D-homosteroid 3 (70%) and chlorohydrin 4 (27%). On the other hand, treatment of la with excess of acetic anhydride and anhydrous ZnCl2 at room temperature leads to reversal of the direction of epoxide ring opening with concomitant methyl migration, leading to 3 beta ,16 alpha -diacetoxy-17-methyl-17 alpha -pregna-5,13-diene-20-one (6) in high yield (92%). The conversions are a remarkable improvement over related routes in terms of both yield and selectivity. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Schwarz,V.; Syhora,K., Collection of Czechoslovak Chemical Communications, 1963, vol. 28, p. 637 - 643
  作者：Schwarz,V.、Syhora,K.

  DOI：——

  日期：——
• Synthesis of novel 1,2,3-triazolyl derivatives of pregnane, androstane and<scp>d</scp>-homoandrostane. Tandem “click” reaction/Cu-catalyzed<scp>d</scp>-homo rearrangement
  作者：Yury N. Kotovshchikov、Gennadij V. Latyshev、Nikolay V. Lukashev、Irina P. Beletskaya

  DOI：10.1039/c4ob00404c

  日期：——

  Copper-catalyzed 1,3-dipolar cycloaddition has been employed in the reaction of steroidal azides with various terminal alkynes. A number of novel 1,2,3-triazolyl derivatives of pregnane, androstane and D-homoandrostane were obtained in high yield (70–98%). The developed synthetic protocols allowed us to attach the triazolyl moiety to both the side chain and the steroidal backbone directly, despite

  铜催化的1，3-偶极环加成已用于甾族叠氮化物与各种末端炔的反应中。以高收率（70-98％）获得了许多新型的孕烷，雄烷酮和D-高雄甾烷的1,2,3-三唑基衍生物。尽管多环系统施加了空间位阻，但发达的合成方案使我们能够将三唑基部分直接连接到侧链和甾族骨架上。Cu（II）的存在显示出在温和条件下引起D-均质重排。合理选择铜预催化剂可以使我们与串联D一起进行“点击”反应-homo重排或在没有此过程的情况下。研究了在Cu（II）催化下16-杂取代的类固醇发生D- homo重排的趋势。
• Selektive Addition von gasf�rmigem Chlorwasserstoff an kristalline Epoxide und Steroid-Epoxide
  作者：Gerd Kaupp、Anke Ulrich、Gerhard Sauer

  DOI：10.1002/prac.19923340503

  日期：——

  Solid epoxides add gaseous HCl or HBr regioselectively and without melting, if the melting points are sufficiently high. Such additions proceed diastereoselectively with chiral epoxides. These gas/solid reactions are compared to similar transformations in solution. One observes interesting reaction sequences in the conversions of steroidal epoxides. Thus, the opening of the epoxide ring may be followed by cationic rearrangements, or it occurs elimination of water, if it creates conjugation to a carbonyl group.