(+/-)-steganol | 41451-71-2

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 木脂素内酯
• 英文名称: (+/-)-steganol
• 英文别名: steganol；(9R,13R,14R)-14-hydroxy-3,4,5-trimethoxy-11,18,20-trioxapentacyclo[13.7.0.02,7.09,13.017,21]docosa-1(22),2,4,6,15,17(21)-hexaen-10-one
• CAS: 41451-71-2；41451-72-3；58800-44-5；58800-46-7；61176-78-1；107439-62-3；107439-63-4；107439-64-5
• 化学式: C₂₂H₂₂O₈
• 分子量: 414.412
• InChiKey: VLOMFQZOMYZLFI-TYILLQQXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  30
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  92.7
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (+/-)-steganol 生成 (5R)-steganacine
  参考文献：
  名称：

  The ambient temperature Ullmann reaction and its application to the total synthesis of (.+-.)-steganacin

  摘要：

  DOI：

  10.1021/ja00522a058
• 作为产物：
  描述：

  5,6,7,8-tetrahydro-1,2,3-trimethoxy-10,11-methylenedioxy-8-oxodibenzocyclooctene-6-carboxylic acid 在 氢氧化钾 、 sodium tetrahydroborate 、 jones reagent 、 水 作用下， 生成 (+/-)-steganol
  参考文献：
  名称：

  The ambient temperature Ullmann reaction and its application to the total synthesis of (.+-.)-steganacin

  摘要：

  DOI：

  10.1021/ja00522a058

文献信息

• Asymmetric total synthesis of natural (-)-and unnatural (+)-steganacin
  作者：Kiyoshi Tomioka、Tsuneo Ishiguro、Yōichi Iitaka、Kenji Koga

  DOI：10.1016/s0040-4020(01)82416-9

  日期：1984.1

  A virtually complete asymmetric control in the synthesis of 2,3-disubstituted butan-4-olide (10) was demonstrated by employing the butenolide (12) as the chiral acceptor for the conjugate 1,4-addition. Highly efficient asymmetric total synthesis of natural (-)- and unnatural (+)-steganacin was accomplished. The absolute stereostructure of natural antitumor steganain was determined to be 1.

  通过使用丁烯内酯（12）作为共轭1,4-加成的手性受体，证明了合成2,3-二取代的丁-4-醇（10）时几乎完全不对称。完成了天然（-）-和非天然（+）-甜菊糖的高效不对称全合成。天然抗肿瘤甜菜碱的绝对立体结构被确定为1。
• Syntheses totales et etudes de lignanes biologiquement actifs. application de l'α-hydroxyalkylation de β-benzyl γ-butyrolactones a la creation des squelettes phenyl tetraline et bisbenzocyclooctadiene—4
  作者：Robert Dhal、Eric Brown、Jean-Pierre Robin

  DOI：10.1016/s0040-4020(01)82447-9

  日期：1983.1

  The biphenyl 16 (obtained from α-bromopiperonal and the aromatic iodide 14 by a modified Ullmann reaction) was cyclized by intramolecular hydroxyalkylation to the isomeric alcohols 17a and 17b. These were oxidized using Jones' reagent, to afford the enol 18a, together with the tautomeric β-ketolactone Decarboxylation of this mixture using barium hydroxide, followed by Jones' oxidation gave the isomeric

  通过分子内羟烷基化将联苯16（通过改良的Ullmann反应从α-溴代戊二醛和芳香族碘化物14中获得）环化为异构醇17a和17b。使用Jones′试剂将它们氧化，得到烯醇18a，以及使用氢氧化钡将该混合物的互变异构体β-酮内酯脱羧，然后进行Jones′氧化，得到异构体γ-酮酸11a和11b。使用Raphael方法将这些化合物转化为（±）-steganone 1，从3，4，5-三甲氧基苯甲醛开始的总收率约为10％，从联苯16开始的总收率为20.7％。。
• Stereoselective reactions. VIII. Stereochemical requirement for the benzylic oxidation of lignan lactone. A highly selective synthesis of the antitumor lignan lactone steganacin by the oxidation of stegane.
  作者：TSUNEO ISHIGURO、HIDEMICHI MIZUGUCHI、KIYOSHI TOMIOKA、KENJI KOGA

  DOI：10.1248/cpb.33.609

  日期：——

  A highly efficient synthesis of the antitumor steganin lignan steganacin (1) was accomplished. Bromination of stegane (7) with N-bromosuccinimide followed by treatment with aqueous tetrahydrofuran afforded steganol (3) in 85% yield. Acetylation of 3 gave 1 in 72% yield. Stegane (7) was also oxidized with 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone in AcOH to give 1 directly in 10% yield. Stereochemical requirements for the benzylic oxidation of dibenzocyclooctadiene lignan lactones are discussed.

  我们完成了抗肿瘤甜菜苷木质素甜菜苷（1）的高效合成。用 N-溴代丁二酰亚胺溴化 stegane (7)，然后用四氢呋喃水溶液处理，可得到 steganol (3)，收率为 85%。对 3 进行乙酰化后得到 1，收率为 72%。Stegane (7) 也在 AcOH 中与 2，3-二氯-5，6-二氰基-1，4-苯醌发生氧化反应，直接得到 1，收率为 10%。讨论了二苯并环辛二烯木质素内酯苄基氧化的立体化学要求。
• Stereoselective reactions. XII Synthesis of antitumor-active steganacin analogs, picrosteganol and epipicrosteganol, by selective isomerization.
  作者：KIYOSHI TOMIOKA、TSUNEO ISHIGURO、YOICHI IITAKA、KENJI KOGA

  DOI：10.1248/cpb.34.1501

  日期：——

  New steganacin analogs with definite absolute configurations, (-)-picro- and (-)-epipicrosteganol, were synthesized by isomerization of (-)-steganol and (-)-episteganol, respectively, at the α-position to the lactone carbonyl. The structure of (-)-epipicrosteganol was confirmed by X-ray crystallographic analysis. Selective epimerization at the C-4 benzylic position was observed upon acidic treatment of (-)-steganacin, giving (-)-episteganacin.

  通过分别在内酯羰基的 α 位上异构化 (-)-十八烷醇和 (-)-表十八烷醇，合成了具有明确绝对构型的新型隐甲星烷酸类似物 (-)-苦味- 和 (-)-表隐甲烷醇。通过X射线晶体学分析证实了(-)-表吡甾烷醇的结构。在对(-)-steganacin进行酸性处理后，观察到C-4苄基位置的选择性差向异构化，得到(-)-episteganacin。
• Stereoselective reactions. XVII. Absolute structure-cytotoxic activity relationships of steganacin congeners and analogs
  作者：Kiyoshi Tomioka、Tsuneo Ishiguro、Hidemichi Mizuguchi、Nobuyasu Komeshima、Kenji Koga、Shigeru Tsukagoshi、Takashi Tsuruo、Tazuko Tashiro、Seiichi Tanida、Toyokazu Kishi

  DOI：10.1021/jm00105a009

  日期：1991.1

  The cytotoxic activities of optically pure and racemic steganacin congeners and analogues against KB cells in culture and the inhibitor activity of cilia regeneration in Tetrahymena were studied with regard to absolute and retative configurations. The stereochemical requirements of dibenzocyclooctadiene lignan lactones for activity were clarified.