(20S)-2α,3α-isopropylidenedioxy-5α-pregnan-6-one-20-carbaldehyde | 174656-33-8

• 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)-2α,3α-isopropylidenedioxy-5α-pregnan-6-one-20-carbaldehyde
• 英文别名: (20S)-2α,3α-isopropylidenedioxy-20-formyl-5α-pregnan-6-one；(2S)-2-[(1S,2R,4R,8S,10S,13S,14S,17R,18S)-2,6,6,18-tetramethyl-11-oxo-5,7-dioxapentacyclo[11.7.0.02,10.04,8.014,18]icosan-17-yl]propanal
• CAS: 174656-33-8
• 化学式: C₂₅H₃₈O₄
• 分子量: 402.574
• InChiKey: DVHOBFRUYDEYLS-LTHZOOPKSA-N

物化性质

• 沸点：
  501.9±50.0 °C(Predicted)
• 密度：
  1.074±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  29
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (20S)-2α,3α-isopropylidenedioxy-5α-pregnan-6-one-20-carbaldehyde 在 palladium on activated charcoal 、 Wilkinson's catalyst 吡啶 、 chromium(VI) oxide 、 lithium aluminium tetrahydride 、 camphor-10-sulfonic acid 、 氢气 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 苯 为溶剂， -75.0~25.0 ℃ 、344.73 kPa 条件下， 反应 113.5h， 生成 芸苔素内酯
  参考文献：
  名称：

  油菜素内酯的改进合成

  摘要：

  从豆甾醇中合成油菜素内酯，总收率为7％。合成的关键步骤是在– 78°C下进行2α，3α-异丙基二烯二氧基-6-oxo-23,24-dinor-5α-cholan-22-al与3-异丙基丁-2-烯内酯的醇醛缩合反应。以高收率得到具有22 R，23 R立体化学的产物。该产物的催化氢化是高度立体选择性的，导致在中间体中所需的24 S立体化学，该中间体很容易转化为油菜素内酯。

  DOI：

  10.1039/p19960000295
• 作为产物：
  描述：

  (22E,24S)-2α,3α-dihydroxy-5α-stigmast-22-en-6-one 在 吡啶 、 四氧化锇 、 N-甲基吲哚酮 、 甲基磺酰胺 、 camphor-10-sulfonic acid 、 碳酸氢钠 、 高碘酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 、 叔丁醇 为溶剂， 反应 169.0h， 生成 (20S)-2α,3α-isopropylidenedioxy-5α-pregnan-6-one-20-carbaldehyde
  参考文献：
  名称：

  油菜素内酯的改进合成

  摘要：

  从豆甾醇中合成油菜素内酯，总收率为7％。合成的关键步骤是在– 78°C下进行2α，3α-异丙基二烯二氧基-6-oxo-23,24-dinor-5α-cholan-22-al与3-异丙基丁-2-烯内酯的醇醛缩合反应。以高收率得到具有22 R，23 R立体化学的产物。该产物的催化氢化是高度立体选择性的，导致在中间体中所需的24 S立体化学，该中间体很容易转化为油菜素内酯。

  DOI：

  10.1039/p19960000295

文献信息

• A new synthesis of brassinosteroids with a cholestane framework based on a highly functionalized starting material
  作者：Irina D. Alshakova、Yuri V. Ermolovich、Vladimir N. Zhabinskii、Vladimir A. Khripach

  DOI：10.1016/j.steroids.2014.08.020

  日期：2015.5

  A new route to the synthesis of minor brassinosteroids with a cholestane framework (28-norcastasterone and 28-norbrassinolide) has been proposed. It makes use of commercially available 24-epicastasterone as a starting material. In addition, [26,26,26-(2)H3]-28-norcastasterone and [26,26,26-(2)H3]-28-norbrassinolide have been prepared as tools for analytical applications. The key steps were regioselective

  已经提出了一种新的合成具有胆甾烷骨架的小油菜素类固醇的新途径（28-去甲甾烯酮和28-去甲油菜素内酯）。它利用可商购的24-表雌甾烷酮作为起始原料。此外，[26,26,26-（2）H3] -28-去甲甾烯酮和[26,26,26-（2）H3] -28-去甲油菜素内酯已被制备为用于分析应用的工具。关键步骤是对24-表雌甾烷酮中的官能团进行区域选择性操纵，22,23-二醇基团的氧化裂解和克莱森重排。
• An improved synthesis of [26-²H₃]castasterone
  作者：Vladimir N. Zhabinskii、Olga V. Gulyakevich、Peter V. Kurman、Polina S. Shabunya、Svetlana A. Fatykhava、Vladimir A. Khripach

  DOI：10.1002/jlcr.3353

  日期：2015.11

  Commercially available epicastasterone has been employed as a starting material for the preparation of [26-2H3]castasterone. The chemical synthesis has been realized in 13 chemical steps and 4.6% total yield. The target compound is intended to be used as internal standard for the quantitative analysis of brassinosteroids.

  市售的表司他酮被用作制备 [26-2H3]castasterone 的起始原料。该化学合成只需 13 个化学步骤，总收率为 4.6%。目标化合物将用作黄铜类固醇定量分析的内标。
• Brassinosteroid-BODIPY conjugates: Design, synthesis, and properties
  作者：Magdalena Malachowska-Ugarte、Claudio Sperduto、Yuri V. Ermolovich、Alina L. Sauchuk、Michal Jurášek、Raisa P. Litvinovskaya、Darya Straltsova、Igor Smolich、Vladimir N. Zhabinskii、Pavel Drašar、Vadim Demidchik、Vladimir A. Khripach

  DOI：10.1016/j.steroids.2015.07.002

  日期：2015.10

  Three BS-BODIPY (brassinosteroids-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) conjugates were synthesized and their fluorescent and immunological properties were investigated. Two of the conjugates, having present all the functional groups characteristic of BS, were shown to be potentially useful as biological probes to study involvement of BS into physiological processes in living cells. (C) 2015 Elsevier Inc. All rights reserved.
• Synthesis of 26,27-bisnorcastasterone analogs and analysis of conformation–activity relationship for brassinolide-like activity
  作者：Shuji Yamamoto、Bunta Watanabe、Junko Otsuki、Yoshiaki Nakagawa、Miki Akamatsu、Hisahi Miyagawa

  DOI：10.1016/j.bmc.2005.10.024

  日期：2006.3

  Three castasterone (CS) derivatives with varied side-chain moieties, 26,27-bisnorcastasterone (20S-bisilorCS), 20-epi-26,27-bisnorcastastcrone (20R-bisnorCS), and 21,26,27-trisnorcastasterone (trisnorCS), were synthesized stereoselectively from either stigmasterol or dehydroisoandrosterone. The 50% effective doses (ED50, nmol/plant) in the concentration-response Curve for brassinolide-like activity in the rice lamina inclination assay were determined to be 0.020 nmol (pED(50) = 10.7) for 20S-bisnorCS, 3.2 nmol (pED50 = 8.5) for 20R-bisnorCS, and 2.0 nmol (pED50 = 8.7) for trisnorCS. An analog containing an ester linkage between the steroid and the side-chain moiety of 20S-bisnorCS was also synthesized and its activity was evaluated to be 3.2 nmol (pED50 = 8.5), being equipotent to 20R-bisnorCS and trisnorCS. The activity of 20S-bisnorCS was 1/40 that of CS. The conformation analysis was conducted using a systematic search, showing that the activity decreases with an increase in the degree of freedom of the side chain of the steroidal skeleton. (c) 2005 Elsevier Ltd. All rights reserved.
• Improved synthesis of brassinolide
  作者：Trevor C. McMorris、Rodrigo G. Chavez、Prakash A. Patil

  DOI：10.1039/p19960000295

  日期：——

  Brassinolide has been synthesized from stigmasterol in an overall yield of 7%. The key step in the synthesis is aldol condensation of 2α,3α-isopropylidenedioxy-6-oxo-23,24-dinor-5α-cholan-22-al with 3-isopropylbut-2-enolide carried out at – 78 °C, which gives a product with 22R,23R stereochemistry in high yield. Catalytic hydrogenation of this product is highly stereoselective leading to the desired

  从豆甾醇中合成油菜素内酯，总收率为7％。合成的关键步骤是在– 78°C下进行2α，3α-异丙基二烯二氧基-6-oxo-23,24-dinor-5α-cholan-22-al与3-异丙基丁-2-烯内酯的醇醛缩合反应。以高收率得到具有22 R，23 R立体化学的产物。该产物的催化氢化是高度立体选择性的，导致在中间体中所需的24 S立体化学，该中间体很容易转化为油菜素内酯。