(20S)-6-(1,3-dioxolan-2-yl)-3α,5-cyclo-20-formyl-5α-pregnane

• 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: (20S)-6-(1,3-dioxolan-2-yl)-3α,5-cyclo-20-formyl-5α-pregnane
• 英文别名: (20S)-6,6-ethylenedioxy-20-formyl-3α,5-cyclo-5α-pregnane；(2S)-2-[(1'S,2'R,5'R,7'R,10'S,11'S,14'R,15'S)-2',15'-dimethylspiro[1,3-dioxolane-2,8'-pentacyclo[8.7.0.02,7.05,7.011,15]heptadecane]-14'-yl]propanal
• 化学式: C₂₄H₃₆O₃
• 分子量: 372.548
• InChiKey: ITWCIOTVSVEPQU-LHHRZECNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (20S)-6-(1,3-dioxolan-2-yl)-3α,5-cyclo-20-formyl-5α-pregnane 在 lithium aluminium tetrahydride 、 硫酸 、 丙酸 、 三乙胺 作用下， 以 四氢呋喃 、 丙酮 、 甲苯 、 xylene 为溶剂， 反应 9.0h， 生成 (22E,24S)-3α,5-cyclo-5α-ergost-22-en-6-one
  参考文献：
  名称：

  Castasterone 和 Brassinolide 的改进合成†

  摘要：

  Castasterone 1 是从已知的 (20S)-6,6-ethylenedioxy-20-formyl-3α,5-cyclo-5α-pregnane 4 以 32% 的总产率通过八个步骤合成的。

  DOI：

  10.1039/a702805i
• 作为产物：
  描述：

  (1'S,2'R,5'R,7'R,10'S,11'S,14'R,15'R)-14'-[(E,2R,5R)-5-ethyl-6-methylhept-3-en-2-yl]-2',15'-dimethylspiro[1,3-dioxolane-2,8'-pentacyclo[8.7.0.02,7.05,7.011,15]heptadecane] 生成 (20S)-6-(1,3-dioxolan-2-yl)-3α,5-cyclo-20-formyl-5α-pregnane
  参考文献：
  名称：

  XRIPACH, V. A.;ZHABINSKIJ, V. N.;OLXOVIK, V. K.;LAXVICH, F. A., ZH. ORGAN. XIMII, 26,(1990) N, S. 1966-1976

  摘要：

  DOI：

文献信息

• A new approach to the side chain formation of 24-alkyl-22-hydroxy steroids: Application to the preparation of early brassinolide biosynthetic precursors
  作者：Alaksiej L. Hurski、Vladimir N. Zhabinskii、Vladimir A. Khripach

  DOI：10.1016/j.steroids.2012.03.010

  日期：2012.6

  introduction of the 22-hydroxyl group has been achieved by epoxidation of the Delta(22)-double bond, nucleophilic opening of the intermediate mesyl epoxide with sodium sulfide, and desulfurization of the formed tetrahydrothiophenes with Raney nickel.

  已开发出一种合成22S-羟基-24R-甲基类固醇的新途径，并将其用于制备油菜素内酯生物合成早期的前体卡他甾酮，（22S）-羟基菜甾醇和6-脱氧卡他甾酮。在C-24处具有正确立体化学的类固醇侧链的构建基于克莱森重排的使用。22-羟基的引入已通过Delta（22）-双键的环氧化，中间体甲磺酰基环氧化物与硫化钠的亲核开环以及所形成的四氢噻吩与阮内镍的脱硫而实现。
• Synthesis of brassinolide and its biosynthetic precursors using methyl 3-hydroxy-2-methylpropionate
  作者：V. A. Khripach、V. N. Zhabinskii、K. V. Parkhimovich、O. V. Gulyakevich

  DOI：10.1134/s1068162009020137

  日期：2009.3

  Formal synthesis of plant hormones that belong to the group of 24α-methylbrassinosteroids, including brassinolide and its biosynthetic precursors with one hydroxyl group in their side chain, was performed. Stereochemistry of a methyl group at the C24 atom was provided by the choice of the desired enanthiomer of methyl-3-hydroxy-2-methylpropionate and by the sequence of its conversions into the chiral

  进行了属于 24α-甲基油菜素类固醇组的植物激素的正式合成，包括油菜素内酯及其侧链具有一个羟基的生物合成前体。C24 原子上甲基的立体化学是通过选择所需的甲基-3-羟基-2-甲基丙酸酯对映异构体及其转化为形成 C23-C28 所必需的手性中间体的顺序来提供的。侧链的片段。(22R,23R)-二醇基团是通过中间体 Δ22-类固醇的 Sharpless 不对称二羟基化引入的，这是低分子砜与类固醇 C22-醛的连接、乙酰化和还原脱硫的连续反应的产物中间体 β-乙酰氧基砜。22-乙酰氧基-23的还原，
• Improved Synthesis of 28-Norbrassinolide
  作者：Vladimir A. Khripach、Vladimir N. Zhabinskii、Yurii V. Ermolovich

  DOI：10.1080/00397910903318757

  日期：2010.8.16

  An improved procedure for the preparation of 28-norbrassinolide is described. The key step of the whole process was the construction of the side-chain carbon skeleton, which was achieved by successive addition of C23–C24 and C25–C27 fragments to 22C-steroidal aldehyde via the Normant reaction and Claisen rearrangement. The method affords the title compound in 16% overall yield from stigmasterol and

  描述了一种用于制备 28-去甲芸苔素内酯的改进程序。整个过程的关键步骤是侧链碳骨架的构建，这是通过通过诺曼特反应和克莱森重排将 C23-C24 和 C25-C27 片段连续添加到 22C-甾体醛上来实现的。该方法从豆甾醇中以 16% 的总产率提供了标题化合物，并且代表了对文献方法的显着改进。
• Synthesis of hexadeuterated 23-dehydroxybrassinosteroids
  作者：Vladimir A. Khripach、Vladimir N. Zhabinskii、Andrey P. Antonchick、Olga V. Konstantinova、Bernd Schneider

  DOI：10.1016/s0039-128x(02)00071-5

  日期：2002.12

  instead of the 22R,23R-diol function characteristic for most compounds of this class were prepared for biochemical studies. The corresponding non-deuterated compounds are considered intermediates in brassinolide biosynthesis. The carbon skeleton of the side chain with proper stereochemistry at C(24) was prepared from commercially available (2R)-3-hydroxy-2-methylpropanoate. This low molecular fragment was

  两个六氘代油菜素类固醇（BS）（[26,27-2H（6）]-23-dehydroxycastasterone和[26,27-2H（6）]-cathasterone）在C（22）处含有羟基而不是22R，23R制备了大多数此类化合物的β-二醇功能特性，用于生化研究。相应的非氘代化合物被认为是油菜素内酯生物合成的中间体。由市售（2R）-3-羟基-2-甲基丙酸酯制备具有适当立体化学的C（24）侧链碳骨架。通过适当的砜与C（22）醛的反应，将该低分子片段与四环甾体片段偶联。22-羟基的必要构型的形成是通过氢化还原相应的酮来实现的。
• Synthesis of secasterol and 24-episecasterol and their toxicity for MCF-7 cells
  作者：V. A. Khripach、V. N. Zhabinskii、O. V. Gulyakevich、O. V. Konstantinova、A. Yu. Misharin、A. R. Mekhtiev、V. P. Timofeev、Ya. V. Tkachev

  DOI：10.1134/s1068162010060117

  日期：2010.11

  The convergent synthesis of biosynthetic precursors of brassinosteroids with a Delta(2)-bond in cycle A-secasterol and 24-episecasterol-was performed. The key stages in the construction of the side chain in these compounds were the Julia olefination of the steroid 22-aldehyde followed by the Sharpless asymmetric dihydroxylation of the intermediate Delta(22)-olefin. The cytotoxicity of the synthesized compounds for breast carcinoma MCF-7 cells was assessed.