(20S)-6,6-ethylenedioxy-2α,3α-isopropylidenedioxy-5α-pregnane-20-carbaldehyde | 81481-15-4

• 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)-6,6-ethylenedioxy-2α,3α-isopropylidenedioxy-5α-pregnane-20-carbaldehyde
• 英文别名: (20S)-6-ethylenedioxy-2α,3α-isopropylidenedioxy-23,24-dinor-5α-cholan-22-al；6,6-ethylenedioxy-2α,3α-isopropylidenedioxy-5α-pregnane-20S-carboxaldehyde；(2R,3S)-2,3-isopropylidenedioxy-6,6-ethylenedioxy-5α-pregnane-20-carboxaldehyde；6,6-ethylenedioxy-20-formyl-2α,3α-isopropylidenedioxy-5α-pregnane；(2R,3S,20S)-2,3-isopropylidenedioxy-6,6-ethylenedioxy-20-formyl-5α-pregnane；(2S)-2-[(1'S,2'R,4'R,8'S,10'S,13'S,14'S,17'R,18'S)-2',6',6',18'-tetramethylspiro[1,3-dioxolane-2,11'-5,7-dioxapentacyclo[11.7.0.02,10.04,8.014,18]icosane]-17'-yl]propanal
• CAS: 81481-15-4
• 化学式: C₂₇H₄₂O₅
• 分子量: 446.627
• InChiKey: LYIXEEDYXYRHQX-MHRQTEEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  32
• 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：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (20S)-6,6-ethylenedioxy-2α,3α-isopropylidenedioxy-5α-pregnane-20-carbaldehyde 在 titanium(IV) isopropylate 、 正丁基锂 、 L-(+)-酒石酸二乙酯 、 三氟过氧乙酸 、 过氧化氢异丙苯 、 4 Angstroem MS 、 双氧水 、 三氟乙酸 作用下， 以 乙醚 、 二氯甲烷 、 氯仿 为溶剂， 反应 175.0h， 生成 芸苔素内酯
  参考文献：
  名称：

  Concise, Improved Procedure for the Synthesis of Brassinolide and Some Novel Side-Chain Analogues

  摘要：

  DOI：

  10.1021/jo961854y
• 作为产物：
  描述：

  2,2-二甲基-1,3-二氧环戊烷 在 对甲苯磺酸 碳酸氢钠 、 臭氧 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 (20S)-6,6-ethylenedioxy-2α,3α-isopropylidenedioxy-5α-pregnane-20-carbaldehyde
  参考文献：
  名称：

  Aburatani, Masakazu; Takeuchi, Tadashi; Mori, Kenji, Agricultural and Biological Chemistry, 1985, vol. 49, # 12, p. 3557 - 3562

  摘要：

  DOI：

文献信息

• Synthesis and configurational assignment of epimeric 22-hydroxy-, 23, 24-acetylenic, olefinic or epoxy steroids using carbon-13 NMR Spectroscopy
  作者：Braja G. Hazra、Vandana S. Pore、Padmakar L. Joshi、Sharmila N. Padalkar、Shubhada A Deshpande、Pattuparambil R. Rajamohanan

  DOI：10.1002/mrc.1260310616

  日期：1993.6

  Stereoisomers of steroidal 22‐hydroxy‐23‐acetylenic, 23‐olefinic and 23, 24‐isomeric epoxides were synthesized from C‐22 aldehydes and their 13C NMR spectra were analysed. A correlation regarding the combined effect of the 22‐hydroxy and 23, 24‐substituents on the stereochemistry of the attached groups at C‐22, ‐23 and ‐24 is derived.

  从 C-22 醛合成了甾体 22-羟基-23-炔属、23-烯烃和 23、24-异构环氧化物的立体异构体，并分析了它们的 13C NMR 光谱。推导出关于 22-羟基和 23、24-取代基对 C-22、-23 和 24 处连接基团立体化学的综合影响的相关性。
• A convenient stereoselective synthesis of castasterone and its analogues using arsenic ylides
  作者：Frédéric Werner、Gilles Parmentier、Bang Luu、Laurence Dinan

  DOI：10.1016/0040-4020(96)00186-x

  日期：1996.4

  22R)-trihydroxy-5α-cholestan-6-one 4 have been synthesized with high stereoselectivity. The key step is the coupling of the aldehyde 5 with an arsenic ylide, followed by an in situ DIBAH reduction. A second arsenic ylide was used to prepare the key allylic alcohol intermediate 15, which allows the synthesis of castasterone 2.

  （2α，3α，22S）-三羟基-5α-胆甾醇-6-one 3和（2α，3α，22R）-三羟基-5α-胆甾醇-6-one 4已经以高的立体选择性合成。关键步骤是将醛5与砷化叶立德偶联，然后进行原位DIBAH还原。第二砷叶立德用于制备关键的烯丙醇中间体15，该中间体允许合成Castasterone 2。
• Brassinolide and its analogs. Part IV. Synthesis of brassinolide analogs with or without the steroidal side chain.
  作者：Michitada KONDO、Kenji MORI

  DOI：10.1271/bbb1961.47.97

  日期：——

  Four brassinolide analogs were synthesized starting from cholesterol, stigmasterol or pregnenolone. An analog possessing a hydroxyl group at C-17 instead of the steroidal side chain was only 0.001% as active as brassinolide upon lamina-inclination testing with rice seedlings, while other analogs were 1-2% as active as brassinolide. This indicates the indispensable role of the side chain for the plant growth-promoting activity of brassino-steroids.

  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。
• Synthesis of naturally occurring brassinosteroids employing cleavage of 23,34-epoxides as key reactions. Synthesis of brassinolide, castasterone, dolicholide, dolichosterone, homodolicholide, homodolichosterone, 6-deoxocastasterone and 6-deoxodolichosterone
  作者：Kenji Mori、Masayuki Sakakibara、Katsuhide Okada

  DOI：10.1016/s0040-4020(01)91129-9

  日期：1984.1

  Eight new plant growth-promoting steroids (brassinolide, castasterone, dolicholide, dolichosterone, homodolicholide, homodolichosterone, 6-deoxocastasterone and 6-deoxodolichosterone) were synthesized by the regio- and stereoselective ring-opening reactions of 23,24-epoxides prepared from stigmasterol.

  通过由白豆甾醇制备的23,24-环氧化合物的区域和立体选择性开环反应合成了八种新的促进植物生长的类固醇（油菜素内酯，蓖麻甾酮，三聚乙内酯，三聚二十碳二烯酮，高二羟乙内酯，高聚雌甾烯酮，6-脱氧基castasterone和6-脱氧二烯基甾烷酮）。
• Synthesis of (22S, 23S)-homobrassinolide and brassinolide from stigmasterol
  作者：Kenji Mori、Masayuki Sakakibara、Yoshitaka Ichikawa、Hiraki Ueda、Katsuhide Okada、Takeaki Umemura、Goro Yabuta、Shigefumi Kuwahara、Michitada Kondo、Masao Minobe、Akemi Sogabe

  DOI：10.1016/0040-4020(82)85157-0

  日期：1982.1

  23S)-Homobrassinolide (2α, 3α, 22S, 23S-tetrahydroxy-24S-etyl-B-homo-7-oxa-5α-cholestan-6-one) and brassinolide (2α, 3α 22R, 23R-tetrahydroxy-24S-methyl-B-homo-7-oxa-5α-cholestan-6-one) were synthesized from stigmasterol and shown to promote plant growth.

  （22 S，23 S）-高油菜素内酯（2α，3α ，22 S，23 S-四羟基-24 S-乙炔基-B-homo-7-oxa-5α-胆甾烷-6-一）和油菜素内酯（2α，3α22 R，23 R-四羟基-24 S-甲基-B-homo-7-oxa-5α-胆甾烷-1-酮）由豆甾醇合成，并显示出促进植物生长的作用。